[Link].

org Article

Si Nanowires Grown on Cu Substrates via the Hot-Wire-Assisted

Vapor−Liquid−Solid Method for Use as Anodes for Li-Ion Batteries
Rashmi Tripathi, Vaishali Chauhan, Pranay Gandharapu, Sushobhan Kobi, Amartya Mukhopadhyay,*
and Rajiv O. Dusane*
Cite This: ACS Appl. Nano Mater. 2022, 5, 17767−17782 Read Online

ACCESS Metrics & More Article Recommendations *

sı Supporting Information
See [Link] for options on how to legitimately share published articles.
Downloaded via INDIAN INST OF TECH BOMBAY on February 28, 2024 at 12:21:20 (UTC).

ABSTRACT: Silicon is a high-capacity and safer next-generation anode

material for Li-ion batteries, with challenges from rapid capacity fade due to
colossal volume changes during Li alloying/de-alloying. Nanostructured Si is
deemed to address the above issue, with the possible usage of Si nanowires
(SiNWs) on copper substrates (sans any binder or conducting additive)
offering the highest performance in terms of anode capacity. However, the
direct growth of SiNW on copper current collector foils is challenging and not
reported earlier. Against this backdrop, we demonstrate here, for the first time,
the successful growth of SiNW, with controllable features, on battery-grade
copper substrates via a hot-wire-assisted vapor−liquid−solid (VLS) route.
The usage of Sn as a nanotemplate has allowed bringing down the growth
temperature to 400 °C, with the SiH4 pressure and growth duration being other crucial parameters controlling various features of
SiNWs, such as length, diameter, aspect ratio, effective crystalline core-to-amorphous shell ratio, morphology of the shell, and
orientation with respect to the substrate. The emphasis here is on the variations of different morphological features of these
nanowires with changes in process conditions as these are bound to have important implications for various electronic applications.
One such application that we explore is their usage as an anode in Li-ion batteries. In the Li “half” cell, the free-standing SiNWs on
copper foil exhibit reversible Li-storage capacities of ∼3556 mAh/g @ C/5 and ∼2462 mAh/g @ 1C while retaining ∼89% of the
capacity after 100 cycles @ 1C. In the Li-ion “full” cell (with a home-made LiFePO4-based cathode), ∼97% capacity retention has
been obtained after 100 cycles @ 341 μA/cm2. The superior electrochemical performance as an anode, the scalability of the growth
technique, and the ability to tune the SiNW characteristics open up the possibility of industrial-scale application of the as-grown
SiNWs on copper foil.
KEYWORDS: Si nanowire growth, vapor−liquid−solid mechanism, Si nanowire features, electrochemical behavior, Li-ion battery,
silicon anode

1. INTRODUCTION with cycling.8−12 The continuous volume expansion and

The application domain of silicon nanowires (SiNWs) expands contraction also aid in the formation and rupture of the solid
from field-effect transistors (FETs), sensors, photovoltaics, electrolyte interface (SEI) layer on the Si anode, thus consuming
more and more Li ions irreversibly and increasing the impedance
electromechanical switches, and memory devices to thermo-
of the cell with charge−discharge cycles.13−15
electric devices, supercapacitors, and batteries. These applica-
Various morphologies and forms of silicon including
tions are utilized either as free-standing nanowires or in the form
amorphous films with thickness varying between a few tens of
of composites.1−5 In the context of battery application, even
nanometers to a few micrometers, nanoparticles, composites,
before the advent of SiNWs, silicon was recognized as a potential
and silicon nanowires have been explored by researchers to
anode material for next-generation Li-ion batteries. This is
facilitate its incorporation in the commercial Li-ion batteries but
because Si can reversibly alloy with Li under the concerned
with limited success.16−20 In general, the 1D silicon (nanowire)
anodic conditions, with the theoretical Li-storage capacity being
has been the most successful in accommodating the volume
an order of magnitude greater than that of the presently used
graphitic carbon. Also, the Li-alloying potential prevents Li-
plating (unlike graphitic carbon).1,6−8 Received: August 24, 2022
However, Si-based anodes suffer from volume expansion/ Revised: November 1, 2022
contraction (by >300%) during Li alloying/de-alloying, which Accepted: November 4, 2022
leads to stress development and concomitant cracking/ Published: December 7, 2022
disintegration, as well as loss of contact with the substrate
(current collector). These cause rapid fade in Li-storage capacity

© 2022 American Chemical Society [Link]

17767 ACS Appl. Nano Mater. 2022, 5, 17767−17782
ACS Applied Nano Materials [Link] Article

Figure 1. (a) Schematic illustration of the SiNW growth process, along with the associated chemistry and resultant core−shell structure; SEM
micrographs of (b) 4 mg of Sn deposited on as-received (cleaned with IPA) copper foils, (c) Sn nanotemplate formed with 4 mg of Sn after atomic
hydrogen treatment at a temperature of 400 °C on the as-received copper foils (cleaned with IPA), (d) randomly oriented SiNWs grown on the as-
received copper foils (cleaned with IPA), (e) 4 mg of Sn deposited on copper foils cleaned with acetic acid (post IPA cleaning) for removing surface
oxide(s), (f) surface of foils cleaned with acetic acid (post IPA cleaning) after atomic hydrogen treatment at 400 °C, indicating the absence of Sn
particles, and (g) no observable SiNW growth on the oxide-free copper foils. The SiNW growth was carried out at a substrate temperature of 400 °C for
15 min at a SiH4 flow rate of 5 sccm and a SiH4 pressure of 30 mTorr.

change while maintaining contact with the current collector, as SiNWs on copper substrates/foils, which forms the motivation
first reported by Chan et al.1 with crystalline SiNWs. Since then, behind the present study.
various studies have focused on understanding the mechanism Since the first report by Wagner and Ellis on the vapor−
of electrochemical lithiation/delithiation in SiNW-based liquid−solid (VLS) mechanism of growth of Si whiskers, the
electrodes, aiming toward increasing the cyclic stability (i.e., method has been employed more frequently by researchers.34
capacity retention over a large number of cycles) and Numerous elements have been used as catalytic templates, such
suppressing the irreversible capacity loss.6,13,21−25 as Au, Al, Cu, Ti, Zn, and Sn, for SiNW growth.35,36 Previous
Interestingly, studies on Si-based films indicate better works from our group have reported the usage of Sn as the
performance by amorphous Si films, as compared to the catalyst/template for SiNW growth on various substrates like
crystalline Si films.26,27 This is attributed to the relatively open glass, silicon, and stainless steel. This exploits the formation of
structure of amorphous Si, albeit with a lower electronic mobility Sn-Si eutectic alloy at a temperature of 232 °C, leading to SiNW
(<10 cm2 V−1 s−128), as compared to crystalline Si (>20 cm2 V−1 growth at fairly low temperatures.31,37−39 The reports cutting
s−1 for poly-Si29). Hence, combining these two, i.e., forming a across all fields of applications of SiNWs grown via the VLS
composite structure by way of developing Si nanowires having a mechanism use the Sn template on various substrates, other than
crystalline Si (c-Si) core and amorphous Si (a-Si) shell, can, in copper, even though copper is the choice of metal for
principle, help retain the high electronic mobility all along the commercial applications as the current collector for batteries,
nanowire length (via the c-Si core) and also better accommodate supercapacitors, sensors, etc.40−44 The lack of a facile one-step
growth of SiNWs on copper complicates the fabrication process
volume changes in the presence of the amorphous Si shell.6
and degrades the Si/substrate interface quality by adding a
Most of the previous work concerning SiNW growth at low
transfer step from other substrates to the copper substrate.3,45
temperature, with Sn as the catalyst, was carried out using
Against this backdrop, in this work the growth of silicon
stainless steel substrates.6,13,30−32 However, for battery
nanowires (SiNWs) directly on battery-grade copper foil, while
application, copper is the preferred choice of substrate for the still using Sn as the catalyst/nanotemplate and a low growth
anode current collector because of its high electrical temperature of 400 °C, has been rendered feasible after carefully
conductivity (1.673 × 10−8 Ωm at 20 °C). Other beneficial studying the various aspects of the Cu/Sn interface and the VLS
aspects of the copper substrate include a high thermal mode of nanowire growth. More details/mechanisms concern-
conductivity (398 W/mK at 25 °C), high melting temperature ing the SiNW growth via the VLS mechanism using hot-wire
(1085 °C), and abundance in Earth’s crust (55−70 ppm).33 chemical vapor deposition (HWCVD; which further facilitates
Furthermore, if SiNWs can be grown on copper, the good lowering of substrate temperature and reducing contamination)
contact at the concerned Si/Cu interface and higher electrical (as Section S1), including a schematic representation in Figure
conductivity may render it possible to use the as-grown SiNWs S1, are presented in the Supporting Information. In addition to
on copper directly as the anode, eliminating the need for a revealing that SiNW growth on copper foil is possible, we also
binder and conducting additives, which will, in turn, raise the bring out the correlation between working pressure, growth time
overall anode capacity and, thus, energy density of the batteries. and the morphology, crystalline/amorphous ratio, growth rate,
It is thus important to develop the process and establish the and microstructure/morphology of the amorphous shell and
recipe for reproducibly growing SiNWs, which are adhered to orientation of the SiNWs with respect to the copper substrate.
the copper substrates, with varied features, at low growth This provides a handle toward tuning the SiNW characteristics,
temperature(s). However, to the best of the authors’ knowledge, as required for a given application. In the context of usage as
there is yet no report concerning the feasibility of growth of anode for Li-ion batteries, the as-grown SiNWs on copper
17768 [Link]
ACS Appl. Nano Mater. 2022, 5, 17767−17782
ACS Applied Nano Materials [Link] Article

substrate (sans any binder or conducting additive) have been time. The SiH4 flow rate was maintained at 3 sccm, the filament
investigated in Li “half” cells, as well as in Li-ion “full” cells, temperature was kept constant at 1650 °C, and the substrate
where a near-theoretical Li-storage capacity (∼3556 mAh/g @ temperature was maintained at 400 °C throughout the process.
C/5), along with excellent reversibility (first cycle coulombic 2.3. Physical Characterizations. The dimensions and morphol-
ogy of Sn nanotemplates before and after the atomic hydrogen
efficiency >93%), rate capability (∼2462 mAh/g @ 1C), and treatment, as well as the morphology of the SiNWs, were observed
cyclic stability (∼89% capacity retention after 100 cycles @ 1C), using a field emission gun scanning electron microscope (Carl Zeiss,
has been achieved. Auriga Compact). The crystalline and amorphous structures of the
SiNWs were studied using X-ray diffraction (XRD) (Smartlab, Rigaku)
2. EXPERIMENTAL DETAILS equipped with high-power (9 kW) Cu Kα radiation of 1.54 Å in
2.1. Preparation of Sn Nanotemplates. The reproducible wavelength, Raman spectroscopy (WITec Alpha 300RS), and trans-
growth of Si nanowires (SiNWs) on battery-grade copper foils is the mission electron microscopy (TEM) (Thermo Scientific Themis 300).
first important aspect of the present work. For this, it was also important X-ray diffraction patterns were recorded at a grazing angle of 0.5°, with a
to establish the right surface conditions of the copper substrates. step size of 0.01° and a scan rate of 2.5° per minute in the 2θ range of
Battery-grade copper foils, with a thickness of ∼12 μm, were cleaned 20−60°. The Raman spectra were recorded using a power of 5 mW for
with isopropyl alcohol (IPA) (Merck, Emparta). Some of the IPA- two accumulations of 60 s each, with a 20× objective lens and a laser of
cleaned copper foils were further dipped in acetic acid (Merck, 100% 532 nm in wavelength. X-ray photoelectron spectroscopy (XPS)
glacial, Emparta) for 5 min to remove the surface oxide(s).46 The X-ray (Kratos Analytical, AXIS Supra) for copper foils was performed to
photoelectron spectroscopy (XPS) survey scan spectra, as in Figure S2 determine the oxide content.
in the Supporting Information, reveal a considerable O content on the 2.4. Electrochemical Characterizations. Copper foils with
surface of the as-received (IPA-cleaned) copper foils, in contrast to the SiNWs grown on them (with 30 mTorr pressure, 5 sccm silane flow,
acetic acid-treated copper foils. After removing from acetic acid, the and 15 min growth duration) were directly cut into circular pieces of 14
foils were rinsed with de-ionized (DI) water. The scanning electron mm in diameter (as free-standing electrodes) and assembled in coin
microscopy (SEM) image of these two sets of copper foils can be seen in cells (CR2032) in an Ar-filled glove box (M Braun Unilab Pro SB). For
Figure S3 in the Supporting Information. These two types of treated fabricating Li “half” cells, the Li metal (99.9%) was used as the counter/
foils (viz., cleaned and surface-treated) were loaded into a physical reference electrode, 1 M LiPF6 in 1:1 (v/v) ethylene carbonate
vapor deposition (PVD) chamber (HHV Ltd. 12A4SC) for deposition (EC):diethyl carbonate (DEC) with 10 wt % fluorinated ethyl
of Sn thin films. The chamber was evacuated to a pressure of 2 × 10−6 carbonate (FEC) was used as the electrolyte (Sigma-Aldrich), and
Torr. Four milligrams of Sn powder (Sigma-Aldrich, 99.8% trace metal polypropylene was used as the separator. After assembly, the cells were
basis, <45 μm particle size) was fully evaporated from a molybdenum held at the open-circuit voltage for 10 h to ensure proper electrode
boat to yield a Sn film with a certain thickness on the copper substrates wetting with the electrolyte. Cyclic voltammetry was performed at a
kept at room temperature. scan rate of 0.1 mV/s within a potential window of 0.05−2 V (vs Li/
2.2. Growth of Silicon Nanowires on Copper Substrate. The Li+) using Autolab204 (Metrohm). Galvanostatic cycling of the “half”
Sn-coated copper foils were then transferred to the hot-wire chemical cells was performed within the same potential window at current
vapor deposition (HWCVD) multichamber cluster tool for atomic densities equivalent to C/5 and 1C for 100 and 350 cycles, respectively,
hydrogen treatment. The details for the usage of the HWCVD process using a Neware battery tester. The cells that were cycled at 1C were first
to carry out this thermal treatment in the presence of atomic hydrogen subjected to “formation cycles” at a current density equivalent to C/10
generated by the heated filament, as well as for growing SiNWs (albeit for five cycles within the same potential window. The rate capability test
on substrates other than Cu), are described in previous works,37,39,47,48 was performed at current density equivalent to C/5, C/2, 1C, 2C, and
as well as in Section S1 in the Supporting Information, which also 5C and again at C/5 for five cycles each in the Neware battery tester.
includes a schematic of the process (in Figure S1). In general, hot-wire- Electrochemical impedance spectroscopy (EIS) was performed (in
assisted VLS facilitates the growth of SiNWs at a lower substrate Biologic BCS-810) for the cells after 1st, 10th, and 100th cycles of
temperature because the dissociation of precursor gas occurs at the hot lithiation/delithiation at current density equivalent to C/5 in the
filament rather than on the substrate surface, unlike in the conventional frequency range of 10 kHz to 10 mHz with the sinusoidal voltage of 10
CVD process as schematically illustrated in Figure 1a. Subsequent to mV amplitude.
this, atomic hydrogen (generated by the hot filament) treatment was Li-ion “full” cells, in the form of CR2032 coin cells, were assembled
carried out for 1 min at a working pressure of 30 mTorr. Hydrogen gas inside the argon-filled glove box with the SiNWs grown on copper foil as
flow was maintained at 30 sccm throughout the process and monitored the anode and home-made LiFePO4-based cathode. More details
using a mass flow controller (MKS Instruments), with the working concerning the LiFePO4-based cathode, which is characterized by
pressure being monitored using a capacitance manometer (MKS LiFePO4 nanoparticles “decorating” multiwalled carbon nanotubes, can
Instruments). Substrates were kept at 400 °C during the hydrogen be found from our previously published work.49 The electrolyte and
treatment. The tantalum filament was held at a temperature of 1750 °C separator used in the “full” cell are the same as in the Li/SiNW “half”
for the generation of atomic hydrogen. The filament temperature was cell. Prior to the “full” cell assembly, the SiNW-based anode was
measured using a two-color pyrometer (Fluke Process Instruments, prelithiated for 45 min. After assembly, the cells were also held at the
Ircon Modline 5). open-circuit voltage for 10 h to ensure proper electrode wetting with the
SiNW growth was initiated immediately after the atomic hydrogen electrolyte. Galvanostatic cycling of the LiFePO4//SiNW “full” cells
treatment in the same chamber without exposing the copper foils to the was carried out in the cell voltage range of 1.2−3.8 V at a current rate
ambient atmosphere. The substrate temperature during SiNW growth equivalent to 1C using the Neware battery tester. The rate capability
was maintained at 400 °C, and the filament temperature was reduced to test was performed at current density equivalent to C/5, C/2, 1C, 2C,
1650 °C. The silane flow was 5 sccm, and the working pressure was 30 and 5C and again at C/5 for five cycles each in the cell voltage range of
mTorr. SiNW growth was carried out for 15 min. 1.2−3.8 V.
To study the effect of variations in gas pressure during the SiNW
growth process, the growth of SiNWs was carried out with the chamber 3. RESULTS AND DISCUSSION
pressure varying between 5 and 30 mTorr. The SiH4 gas flow of 3 sccm 3.1. Understanding the Growth of Silicon Nanowires
was maintained, and the filament was kept at 1650 °C during the SiNW
growth. The substrate was kept at 400 °C throughout the process of on Copper Substrate. The morphologies of 4 mg equivalent
atomic hydrogen treatment and SiNW growth. of Sn film deposited on the copper foils, without and with acetic
In another set of experiment, SiNWs were grown for different acid treatment, are shown in Figure 1b,e, respectively. It can be
durations, varying between 15 and 120 min. A working pressure of 10 seen that the Sn film forms the typical island structure, rather
mTorr was used while studying the effect of variation in the growth than a continuous film on both types of copper substrates. As
17769 [Link]
ACS Appl. Nano Mater. 2022, 5, 17767−17782
ACS Applied Nano Materials [Link] Article

Figure 2. (a) X-ray diffractogram of the SiNWs grown on the copper substrate showing the presence of various crystallographic planes of the SiNWs,
along with the peaks from the copper substrate, (b) Raman spectrum of the SiNWs grown on the copper substrate showing the amorphous hump at
480 cm−1 and the peak at 504 cm−1, representing crystallinity in the SiNWs, (c) TEM image of a single SiNW, (d) higher magnification TEM image of a
SiNW, with the inset showing the diffraction pattern obtained from the encircled region, and (e) high-resolution TEM image showing the crystalline Si
(c-Si) core and amorphous Si (a-Si) shell. The SiNW growth was carried out at a substrate temperature of 400 °C for 15 min at a SiH4 flow rate of 5
sccm and a SiH4 pressure of 30 mTorr.

explained in our previously published work,47 the formation of 44 nm to practically disappearing on the acetic acid-treated
the Sn nanotemplate, i.e., well-distributed Sn nanospheres, copper foils, viz., sans native surface oxide. The increase in size of
requires a combination of (a) weaker adhesion of Sn to the the Sn nanoparticles takes place at the expense of smaller ones,
substrate and (b) higher binding energy between the Sn−Sn as per the Ostwald ripening phenomenon.35,53
atoms. We have shown that atomic hydrogen treatment also aids After the atomic hydrogen treatment, SiH4 flow was initiated
in the formation of such nanospheres along with reduction of tin for the growth of SiNWs. For the foils cleaned with acetic acid to
oxide present on Sn. These spheres then can act as a remove the native surface oxide(s), and concomitantly lacking
nanotemplate to enable the growth of SiNWs by the VLS the presence of Sn nanotemplates post atomic hydrogen
mechanism. The as-deposited Sn islands are 32 (±8) nm in size treatment, only a silicon film got deposited, rather than SiNW,
on the as-received (IPA-cleaned) copper foils. By contrast, the as can be seen from Figure 1g. While acetic acid removes native
Sn islands on the acetic acid-treated copper foils, viz., free of oxide(s) from the surface of copper46 (see Figure S2 in the
native surface oxides,46 are larger in size (∼44 (±6) nm) and Supporting Information), thus allowing Sn to directly interact
relatively more distributed on the substrate surface. We believe with copper, for the as-received copper foils (without acetic acid
that the absence of the copper oxide interlayer (the acetic acid- treatment), the native oxide acts as a barrier between the two. As
treated Cu) promotes the wetting of Sn on copper, leading to per the Cu-Sn phase diagram,55 at our processing temperature of
large-size Sn islands on the surface. This difference is 400 °C, ∼13.8 wt % Sn is soluble in Cu. There are lots of reports
understandable on the basis that copper has a surface energy available in the literature concerning the formation of Sn-Cu
of ≥1.28 J/m2,50 whereas the most stable copper oxide has a intermetallic compounds due to interdiffusion of the elements at
surface energy of 0.76 J/m2.51 even relatively lower temperatures (viz., even from room
Before proceeding with the nanowire growth process, the Sn temperature to 250 °C).56−58 In light of this information and
templates were treated with atomic hydrogen at 400 °C to our SEM observations, we believe that the Sn template does not
remove any surface oxide on the Sn particles that may form remain on the surface at our processing temperature due to
during exposure to the ambient atmosphere.39,52Figure 1c,f alloying between Sn and Cu in the case of the acetic acid-treated
shows the SEM micrographs of the as-received copper foils copper foils, which have negligible surface oxide. Now, since
having native surface oxide(s) (i.e., IPA-cleaned) and copper there are no Sn nanoparticles on the substrate to grow SiNWs,
foils without native surface oxide (i.e., acetic acid-treated post only deposition of the amorphous silicon film takes place, and
IPA cleaning46) (as per XPS data in Figure S2 in the Supporting this is perhaps the reason that the growth of SiNW on copper foil
Information), respectively, after atomic hydrogen treatment. An via the VLS route has never been reported before.
increase in the average diameter of the Sn template from 32 to 34 On the other hand, as can be seen from Figure 1d, exposure to
(±10) nm was observed on the as-received copper foils and from SiH4 after atomic hydrogen treatment promotes the growth of a
17770 [Link]
ACS Appl. Nano Mater. 2022, 5, 17767−17782
ACS Applied Nano Materials [Link] Article

Figure 3. Top-view SEM images of SiNWs grown on copper foil at 400 °C for 30 min with 3 sccm SiH4 flow rate and variable SiH4 pressures of (a) 5
mTorr, (b) 10 mTorr, (c) 20 mTorr, and (d) 30 mTorr. The corresponding cross-sectional SEM images for the SiNWs grown with the variable SiH4
pressures are presented for (e) 5 mTorr, (f) 10 mTorr, (g) 20 mTorr, and (h) 30 mTorr. Variations of (i) length (black pentagram), diameter (cyan
spheres), and (j) aspect ratio (i.e., length/diameter) with the SiH4 gas pressure for the SiNWs grown on copper foil at 400 °C for 30 min with 3 sccm
SiH4 flow rate but with variable SiH4 gas pressures.

dense forest of SiNWs on the as-received copper foils (viz., those on copper foil via the VLS mechanism, which can have a lot of
with native surface oxide; see Figure S2 in the Supporting applications.
Information). This result has immense significance since it 3.2. Characteristics of Silicon Nanowires Grown on
reveals that a simple adjustment can enable the growth of SiNW Copper Substrate. The hot-wire-assisted VLS growth leads to
17771 [Link]
ACS Appl. Nano Mater. 2022, 5, 17767−17782
ACS Applied Nano Materials [Link] Article

Figure 4. Raman spectra of the SiNWs grown on copper foil at 400 °C for 30 min with 3 sccm SiH4 flow rate and varying SiH4 pressures of (a) 5 mTorr,
(b) 10 mTorr, (c) 20 mTorr, and (d) 30 mTorr.

the formation of SiNWs, which are thicker at the base and also been observed through TEM by Soam et al.30 This is also
thinner toward the top, resembling grass-like morphology. This possibly another reason for the appearance of the XRD peak
is because as the growth of the c-Si core of the SiNWs proceeds from more than one plane of the c-Si component. The
as per the VLS mechanism, the additional Si, which gets contribution from the amorphous Si shell appears as a hump
generated continuously by the dissociation of SiH4 at the hot at 480 cm−1.
filament, gets deposited around the periphery of the crystalline The TEM image in Figure 2c shows the grass-like morphology
core in the form of an a-Si:H layer. The SiNWs shown in Figure of the SiNWs, with the diameter decreasing from the base to the
1d have an average length of 3 (±0.84) μm and an average top, while the higher magnification image in Figure 2d reveals a
diameter of 161 (±36) nm, measured at half the length. contrast between the c-Si core and the a-Si shell surrounding it.
The X-ray diffractogram (as in Figure 2a) shows signature The selected area diffraction pattern (SADP), as an inset of
peaks for crystalline Si (c-Si), along with the peak for copper Figure 2d, is comprised of spots arising from the lattice planes of
from the substrate. Multiple Si peaks corresponding to the Si the c-Si core, and the diffused ring around the central spot is the
(111), Si (220), and Si (311) planes can be observed within 20− contribution from the a-Si shell. The high-resolution TEM
60° possibly due to the fairly random orientation of the as-grown image, as in Figure 2e, reveals a clear distinction between the c-Si
SiNWs. Indeed, multiple orientations of Si in the VLS-grown core and the a-Si shell regions.
nanowire have been observed in the selected area diffraction 3.3. Tuning the Orientation of Silicon Nanowires on
pattern (SADP) obtained from the shell of VLS-grown SiNWs in Copper Substrate. SEM images of the SiNWs grown on
previous studies as well.30,59 copper foils at different SiH4 pressures are shown in Figure 3a−
Since hot-wire-assisted VLS growth yields a composite of h. The SEM images show a change in morphology with respect
crystalline Si (c-Si) core and amorphous Si (a-Si) shell to the orientation of the SiNWs as pressure increases. At lower
structure,31 all the first-order Raman vibrations are observed pressures (i.e., 5 and 10 mTorr), the SiNWs are oriented
due to the breakdown of the k-selection rule in the a-Si:H shell. perpendicular to the substrate with only a few nanowires having
The Raman spectrum shown in Figure 2b was deconvoluted and kinks. By contrast, at the higher pressures (i.e., 20 and 30
fitted for first-order Raman scattering for transverse acoustic mTorr), the nanowires become more and more randomly
(TA) vibrational mode at 150 cm−1, longitudinal acoustic (LA) oriented with respect to the substrate. At 20 mTorr pressure, a
vibrational mode at 295 cm−1, longitudinal acoustic (LO) few of the SiNWs can be seen to have a perpendicular
vibrational mode at 480 cm−1, and shifted transverse optical orientation but with the majority having kinks. Furthermore, at
(TO) vibrational mode at 504 cm−1.60 The TO peak appearing 30 mTorr pressure, nearly all the nanowires possess a random
at 520 cm−1 for single-crystal Si is shifted to 504 cm−1, which orientation, exhibiting grass-like morphology, with none of the
indicates the presence of nanocrystalline regions in the SiNWs as nanowires having a perpendicular orientation. Previous work
discussed in ref 61. This nanocrystalline Si in the nanowires has from our group related to the orientation of SiNWs on stainless
17772 [Link]
ACS Appl. Nano Mater. 2022, 5, 17767−17782
ACS Applied Nano Materials [Link] Article

Figure 5. TEM images, SAED patterns (as insets), and HRTEM images obtained with the SiNWs grown at SiH4 pressures of (a−d) 5 mTorr, (e−h) 10
mTorr, (i−l) 20 mTorr, and (m−p) 30 mTorr.

steel substrates also shows a similar trend with an increase in The X-ray diffractograms of the SiNWs grown at all the SiH4
SiH4 pressure.30 gas pressures again show the signature c-Si peaks corresponding
From the cross-sectional SEM images, the variations in the to the Si (111), Si (220), and Si (311) planes (as in Figure S4 in
length and diameter of SiNWs with increasing SiH4 pressure the Supporting Information). The corresponding Raman
were measured, leading to the determination of the aspect ratio spectra (as in Figure 4a−d) show all the first-order Raman
(as in Figure 3i,j). For a constant growth time of 30 min, the vibrations, viz., the TA and LA peaks at ∼150 and ∼294 cm−1,
average length of the SiNWs increases linearly from 3.3 (±0.6) respectively. The broad TO peak, which is usually centered at
μm at a pressure of 5 mTorr to 5.5 (±1.4) μm at a pressure of 20 480 cm−1 and is a signature for amorphous Si, is shifted to lower
mTorr. However, at 30 mTorr pressure, the average length of the values between 468 and 479 cm−1 in our case because of the
SiNWs gets marginally reduced to 4.6 (±1.5) μm. We attribute poor short-range order in the peripheral a-Si:H shell.60 The
this apparent decrease in the average length of the SiNWs at the sharp c-Si peak, which usually appears at 520 cm−1, has been
highest pressure to the “shadowing” effect of the bent SiNWs shifted to ∼500 cm−1. This shift is due to the reasons discussed
with a random orientation, thus obstructing fresh Si atoms to in Section 3.2 and the fact that our SiNWs comprise of a thin
reach the still growing SiNWs. The average diameter of the crystalline Si core surrounded by a thicker amorphous Si shell
SiNWs did not vary much with pressure and remained in and the presence of silicon with multiple nanocrystalline
between 191 and 223 nm; however, a lower average diameter of domains of different crystallographic orientations (as supported
161 (±44) nm was observed at 10 mTorr pressure. An aspect in Figure S4 in the Supporting Information and as observed in
ratio of 25 was achieved for the SiNWs grown at 10 and 20 ref 30). Such peak shifts in nanocrystalline Si have also been
mTorr pressures by the hot-wire-assisted VLS growth method observed by Kravets and Kolmykova.61 The c-Si peak for the
employed here. SiNWs grown at 30 mTorr pressure is highly suppressed due to
17773 [Link]
ACS Appl. Nano Mater. 2022, 5, 17767−17782
ACS Applied Nano Materials [Link] Article

Figure 6. Plots depicting the variations of (a) the estimated values of residence time (black square) and impingement flux (violet pentagon) of silane
gas versus silane pressure and (b) the axial (black diamonds), as well as radial (violet spheres) growth rate versus the silane pressure.

the presence of a thicker amorphous shell surrounding the At higher pressures, i.e., 20 and 30 mTorr, a majority of the Si
crystalline core. nanowires get bent, exhibit kinks in their structure, and no
3.4. Detailed Microstructural Features of Differently longer remain perpendicular to the substrate. Figure 5i shows
Orientated Silicon Nanowires. XRD and Raman spectros- the TEM image of a SiNW grown at 20 mTorr SiH4 pressure,
copy provided some insights into the structural aspects of the where a kink can be seen toward the top. The diffraction pattern
SiNWs grown at the different growth pressures (as in the again shows a combination of spots, broad rings, and halo (viz.,
previous section). Further investigations into the microstructure diffused pattern), with the broad ring/halo being a little more
were conducted using TEM, as presented in Figure 5. Figure 5a prominent in this case due to the higher content of the
shows a low-magnification image of the SiNW grown at 5 mTorr amorphous component in the shell. Figure 5j shows the c-Si core
SiH4 pressure. The nanowire appears to be straight, with rough with an amorphous shell uniformly surrounding it. The HRTEM
edges. The inset shows the SADP, which is a combination of image of the crystalline core (as in Figure 5k) indicates a regular
spots arising from the c-Si planes of the core and faint diffused arrangement of atoms, but with a few defect substructures, in the
rings from the a-Si shell. Figure 5b shows that the c-Si core is form of twins and/or stacking faults, as can be clearly seen from
surrounded uniformly by a mixed phase a-Si shell, containing the inset. It is possible that these defects are associated with the
nanocrystalline grains that form due to local epitaxy on the c-Si kinks, leading to a different growth direction at higher SiH4
core surface, giving the appearance of “columnar” growth. Such pressures. Westwater et al.64 argue that such defects and,
local, noncontinuous, and defective epitaxy has been observed consequently, the kinks are formed at higher pressures due to the
by Tang et al.54 for Sn-catalyzed SiNW grown by PECVD on a instabilities at the liquid Sn and solid SiNW interface. The
glass substrate. A similar epitaxial growth of multicrystalline Si HRTEM image obtained from another region (as in Figure 5l)
films on the crystalline Si substrate (at 175 °C) was also indicates the existence of strain in the c-Si atomic arrangement.
observed by Cabarrocas et al.62 The HRTEM images in Figure
In the case of the 30 mTorr growth pressure, TEM observation
5c,d show a regular arrangement of atoms in the core (as in a
indicates that the nanowires are not straight at all and also have
crystalline material) and the presence of microcrystalline regions
grass-like (tapering) morphology (see Figure 5m). The
embedded in the shell for the SiNWs grown at 5 mTorr.
Now, we try to understand the microstructure of the SiNW diffraction pattern again indicates a c-Si core and a-Si shell.
grown at 10 mTorr by looking at the TEM images at different Additionally, due to the bent morphology of these nanowires,
magnifications. Figure 5e shows the low-magnification TEM the side of SiNW facing the hot-wire and so exposed to the Si-
image of a SiNW grown at 10 mTorr SiH4 pressure. These flux has a thicker shell, whereas the other side has a thinner shell,
nanowires too were straight, had rough edges, and exhibited a as can be seen from Figure 5n. HRTEM images were obtained
somewhat “columnar” growth of the shell. The diffraction from two different regions in the nanowire core, as presented in
pattern shows spots arising from the c-Si planes in the nanowire Figure 5o,p. Defect substructures, primarily in the form of twins
core and faint diffused rings arising from the thin amorphous in the otherwise periodic crystalline arrangement, as well as
shell. Now, the HRTEM image of this nanowire (Figure 5f) strained regions can be clearly seen in Figure 5o, with the
shows that the crystalline core is surrounded by a uniform streaking of the diffraction spots in the inset of Figure 5m being a
amorphous shell. The HRTEM images obtained close to the manifestation of such lattice strains. Nevertheless, some regions
center and edge of the nanowire are shown in Figure 5g,h, of the nanowire core have a perfect periodic arrangement of the
respectively. While the HRTEM image obtained from the core atoms, sans defects, as can be seen in Figure 5p. Overall,
region displays clear lattice fringes corresponding to the correlation of the XRD, Raman spectroscopy, and TEM/
crystalline arrangement of atoms and lattice planes, the HRTEM results reveals that with the increase in SiH4 gas
HRTEM image corresponding to the shell shows embedded pressure, the c-Si core became more defective, whereas the
nanocrystalline regions, similar to the ones grown at 5 mTorr surrounding a-Si shell transformed from being a mixed
SiH4 pressure. The nanowire shells deposited at the lower amorphous-nanocrystalline film at the lower pressures to an
growth pressure have nanocrystalline Si regions, which is typical almost amorphous film at the higher pressures. As the shell
of Si films deposited at low pressures.63 deposition is a continuous and integral process that occurs
17774 [Link]
ACS Appl. Nano Mater. 2022, 5, 17767−17782
ACS Applied Nano Materials [Link] Article

Figure 7. (a) Plot showing the variations of the length (black pentagram) and diameter (cyan spheres) of the SiNWs with growth time. For these SiNW
growth experiments, the temperature was maintained at 400 °C, a SiH4 flow rate of 3 sccm, and a SiH4 pressure of 10 mTorr. The values in the plots are
based on measurements made with corresponding SEM images, some of which are presented in Figure S5 in the Supporting Information. (b) Variation
of the aspect ratio (black half-empty circle) and c-Si/a-Si ratio (green half-filled square) of the SiNWs with the growth time. (c) Variation of the axial
growth rate (black diamond) and radial growth rate (violet circle) of the SiNWs with the growth time. The colored bars represent the different regimes
of growth for c-Si and a-Si. The values in the plots (b) and (c) have been estimated from the measured values, as in plot (a).

during the growth of the SiNWs, we do not expect any chemical The residence time (tres) of a gas species in a chamber is given
modifications to occur at the interface. by:
3.5. Understanding the Effect of SiH4 Pressure on the
Orientation and Characteristics of Silicon Nanowires. To Vch (cm 3) Pg(Pa)
understand the above effect of the SiH4 pressure, the sequence of tres(s) = 5.92 × 10−4
Q o(sccm) (1)
events that lead to the formation of SiNW needs a look into. The
SiH4 gas is made to impinge on the heated filament where it where Vch is the volume of the vacuum chamber in cm3, Pg is the
undergoes a dissociation to Si and 4H. Thus, we have Si atoms pressure in the vacuum chamber in Pa, and Q0 is the gas flow rate
and hydrogen atoms along with the undissociated SiH4 in sccm.65
molecules present in the reactor. In another study (to be Using this equation, the values for the residence time of SiH4
reported separately), we found that the impingement of only species have been presented (as black squares) as a function of
SiH4 on the Sn nanotemplate at this temperature does not lead total gas pressure in Figure 6a. The residence time of the SiH4
to nanowire formation. Moreover, we feel that the modifications species increases linearly with increasing pressure. Accordingly,
in the process conditions during the hot-wire-assisted nanowire the extent of dissociation of SH4 on the filament also increases,
formation could significantly change the morphology and leading to an increase in the number of Si and H atoms, which, in
microstructure of the nanowires. As mentioned above, we turn, impinge on the Sn nanotemplate, leading to SiNW growth.
have Si atoms and hydrogen atoms, along with the undissociated The Si radical, upon impinging on the Sn nanoparticle, gets
SiH4 molecules, in the reactor. The undissociated SiH4 “absorbed” as per the VLS mechanism, resulting in SiNW
molecules and dissociated radicals have different residence growth. Hence, it is the rate of the impingement (Ø) of the Si
times, which is one of the key parameters for film growth or atoms on the Sn nanotemplate, which is the key to the rate of
nanowire formation. The higher the residence time of SiH4 SiNW growth. However, the number of Si atoms formed is
inside the deposition chamber, the higher will be the chances of proportional to the number of SiH4 molecules impinging on the
its dissociation at the filament, leading to generation of a greater heated filament and getting dissociated. This is given by the
number of Si species contributing to the SiNW growth. following formula:
17775 [Link]
ACS Appl. Nano Mater. 2022, 5, 17767−17782
ACS Applied Nano Materials [Link] Article

P the flow of SiH4 gas for a longer time, the thickness of the shell
Ø = 3.513 × 1022 molecules cm−2 s−1
(MT )1/2
(2) deposited around the core keeps on increasing, thus leading to
an increase in the overall diameter of the SiNWs. As mentioned
where P is the pressure in Torr, M is the molecular weight of the earlier, the SiNWs grown via the hot-wire-assisted VLS
species, and T is the temperature in Kelvin.66 mechanism have a tapered shape, viz., a thicker base and a
Based on eq 2, the values of gas impingement flux at the sharper tip. This tapering is the most prominent for a growth
different SiH4 pressures are estimated and presented in Figure 6a duration of 15 min, with a reduction in tapering along the length
(violet pentagon), where one can observe a linear increase in gas as the growth duration increases. In our hot-wire-assisted VLS
impingement flux with increasing growth pressure. Thus, at the growth process, the Sn nanotemplate defines the diameter of the
lower SiH4 pressures (i.e., 5 and 10 mTorr), the residence time of c-Si core, with a large amount of a-Si being deposited
SiH4 and its impingement rate remain low, resulting in the low simultaneously around the growing c-Si core as the a-Si shell.
concentration of the Si radicals, thereby leading to the formation Consequently, the overall diameter of the SiNW (i.e., c-Si core +
of a defect-free core due to the relatively slow growth rates (see a-Si shell) becomes increasingly uniform along the length of the
Figure 6b) and thus forming straight nanowires. The nanowire as the growth proceeds for a duration of 90 min. When
concomitant slow rate of the Si film deposition around the the growth duration is further increased to 120 min, a-Si is
periphery of the nanowire results in an amorphous-nanocrystal- further deposited in a “bulb” form at the tip of nanowires,
line film. The radial growth rate decreases at 10 mTorr, as the Si causing the observed shape to be no longer tapered. More
radicals are consumed in the crystalline core growth. For the importantly, the SiNWs are perpendicular to the substrates for
higher SiH4 pressures (i.e., 20 and 30 mTorr), the residence all the time durations, indicating that the growth duration does
time, as well as the impingement rate of SiH4 on the filament, not influence the defect formation. In another study by Tang et
increases, thereby increasing the dissociation rate and, al.,54 SiNWs grown for 8 h were observed to possess an inverted
subsequently, the rate of SiNW growth, thus yielding a larger conical shape, which is somewhat similar to our SiNWs grown
average length of the SiNWs (see Figure 6b). However, a higher for 120 min, but those nanowires were not oriented
SiNW growth rate results in the formation of defects in the c-Si perpendicular to the substrate, rendering them less suited for
core, causing kinks and resulting in the observed grass-like applications, such as supercapacitor electrodes.2,30
morphology (see Figures 3g,h and 5m). Also, a high dissociation In the context of the aspect ratio of our SiNWs for the
rate of SiH4 leads to deposition of a thicker a-Si film around the different growth durations, as shown in Figure 7b (black half-
SiNW periphery. empty circle), a high aspect ratio of 25 was obtained for a growth
3.6. Tuning the Length and Diameter of Silicon duration of 30 min, following which it decreased to 21 for 45 min
Nanowires. For SiNWs to be used as anode material for Li- and to 15 for 90 min, which then remained constant for up to
ion batteries, the c-Si (core)-to-a-Si (shell) ratio and aspect ratio 120 min of growth duration. Furthermore, ratios of the c-Si core
are important characteristics that necessitate identification and to a-Si shell thickness were estimated, assuming a constant
tuning of process conditions that would enable achieving the diameter of 50 nm for the c-Si core for all the growth durations
desired features. Considering that the growth rates of the core under similar conditions. As expected, the a-Si/c-Si ratio
and shell show different dependences on the process conditions, increases fairly rapidly with a growth duration of up to ∼45
the growth duration was varied from 15 to 120 min (keeping all min, beyond which it remains more or less constant, as shown in
other conditions the same), with the results presented in Figure Figure 7b (green half-filled square), which may act as a guide for
S5 in the Supporting Information (in the form of cross-sectional applications requiring a specific ratio of the c-Si core to a-Si shell.
SEM images) and Figure 7 (as plots). A linear increase in the Based on the growth rate of SiNW in the axial and radial
average length of the SiNWs from ∼1.2 (± 0.2) μm for 15 min to directions, the growth process can be divided into four different
∼10.4 (± 3.3) μm for 90 min has been observed, with, however, regimes. First is the nucleation phase, where the gaseous Si
a drop in the same to ∼8.6 (± 3.4) μm upon a further increase in dissolves in Sn, supersaturates the Sn-Si alloy droplet, and leads
the duration to 120 min (see Figure 7a). In an earlier work, Rathi to precipitation of SiNW. Second is the growth regime where the
et al.52 reported the saturation in the length of SiNWs grown by c-Si core growth is predominant with a minimal amount of a-Si
the PECVD process due to consumption of the Sn template after shell deposition. Third is the regime where the growth of the c-Si
40 min, but in this case, the SiNWs seem to keep growing for core and a-Si shell becomes competitive. Last is the regime
longer duration. The SEM micrograph in Figure S5f in the where the a-Si shell deposition is predominant over the growth
Supporting Information indicates the formation of a bulb-type of the c-Si core. For our growth conditions, the nucleation of
structure at the tips of some of the SiNWs, which have grown up SiNWs occurs within a few minutes (subsequent to dissolution
to ∼14 μm in length for the growth duration of 120 min. and precipitation) of exposure to Si flux, following which the c-Si
However, a bunch of nanowires with a length of only ∼5 μm can growth proceeds with very less amount of a-Si shell deposition
also be observed, implying a bimodal distribution of SiNW taking place. In this regime, the increase in axial growth rate is
lengths for a growth duration of 120 min. It is apparent that these not significant because the (i) flux of Si is consumed in the
smaller nanowires were shadowed by the longer nanowires (with supersaturation of the Sn-Si alloy droplet, enabling the
the bulb-like feature at the top), thus not allowing fresh Si atoms nucleation of SiNWs, and (ii) the diameter of the nanowire
to reach, resulting in a saturation/slight decrease in average increases only after a certain length where the peripheral surface
length. is available for the deposition of the shell. The second regime of
The average diameter of the SiNWs (measured at half the growth lasts for up to ∼45 min, following which the axial growth
length) tends to follow the same trend as the length in the sense and radial deposition take place at their respective rates for up to
that a linear increase in diameter with a growth duration of up to ∼80 min. Here, the radial growth rate is not increasing since the
90 min is followed by a decrease for the growth duration of 120 Sn nanotemplate consumes the incoming flux of Si and thus
min (see Figure 7a). Just like the length, even the diameter of contributes to an increased axial growth rate. A slight decrease in
these nanowires had a kind of bimodal distribution. By allowing axial and radial growth rate was observed for a growth duration
17776 [Link]
ACS Appl. Nano Mater. 2022, 5, 17767−17782
ACS Applied Nano Materials [Link] Article

Figure 8. (a) Cyclic voltammograms obtained with the Si-based electrode comprising of SiNWs grown on copper current collector foil in Li “half” cell
at a potential scan rate of 0.1 mV/s within the potential window of 0.05−2 V (vs Li/Li+). Galvanostatic discharge/charge profiles of the SiNW-based
electrodes in the Li “half” cell at a current density equivalent to (b) C/5 and (c) 1C rate within the potential window of 0.05−2 V (vs Li/Li+).
Variations of the delithiation/reversible capacity (as black spheres) and coulombic efficiency (as olive spheres) with the galvanostatic cycle number of
the free-standing SiNW-based electrodes (i.e., SiNWs grown on copper current collector) in Li “half” cell within the potential window of 0.05−2 V at
current densities equivalent to (d) C/5 for 100 cycles and (e) 1C for 350 cycles.

of 60 min, which is because the morphology of the SiNWs electrochemical lithiation/delithiation was carried out for the
changes from conical (with sharper tips) to cylindrical (Figures randomly oriented SiNWs grown on copper foils (at a fairly high
S5c,d in the Supporting Information). After ∼90 min of growth growth rate; see Sections 2.4 and 3.1), having an average
duration, the radial deposition rate increases as the further flux of diameter of 161 nm and an average length of 3 μm. The cyclic
available Si deposits around in the form of a shell, leading to a voltammograms (within 2−0.05 V; vs Li/Li+), as presented in
higher radial growth rate; consequently, the a-Si shell deposition Figure 8a, present features that are typical of lithiation/
starts dominating over the c-Si core growth, and simultaneously, delithiation of Si-based electrodes. The relatively sharp cathodic
the rate of the increase in length begins to saturate. These peak in the first scan (i.e., lithiation) is primarily due to the
regimes are indicated in Figure 7c, along with the axial and radial presence of a crystalline Si core and short-range order of the
growth rates for the different time durations. amorphous silicon shell in the as-grown condition, leading to the
3.7. Electrochemical Behavior of Free-Standing SiNW formation of Li3.16Si, as reported by Reyes Jiménez et al.67 The
Electrodes in Li “Half” Cell. As a first set of study concerning disruption of the short-range order in the shell upon the first
the applicability of our SiNWs as Li battery anode material, lithiation results in the appearance of mainly broader peaks from
17777 [Link]
ACS Appl. Nano Mater. 2022, 5, 17767−17782
ACS Applied Nano Materials [Link] Article

Figure 9. (a) Galvanostatic charge−discharge (voltage) profiles obtained with the Li-ion “full” cells, fabricated using the free-standing SiNWs grown
on copper current collector as the anode and home-made LiFePO4 as the cathode @ 341 μA/cm2 within the voltage window of 1.2−3.8 V. (b)
Variations of the discharge capacity (black spheres) and coulombic efficiency (olive spheres) with the cycle number for 100 galvanostatic cycles. (c) An
array of 61 red LEDs lit up and (d) a commercial calculator run with the help of the SiNW//LiFePO4 Li-ion “full” cells.

the second lithiation onward. In the first anodic scan (i.e., obtained, which is very close to the theoretical capacity (of
delithiation), the two broad peaks at 0.33 and 0.47 V correspond ∼3600 mAh/g) within the concerned potential window of
to partial and complete delithiation, viz., from Li3.16Si to Li7Si3 0.05−2 V (vs Li/Li+). It reduced marginally to 3361 mAh/g in
and finally from Li7Si3 to LiSi, respectively.13,67 Any noticeable the next cycle and retained ∼77% of the first cycle delithiation
peak for reduction/decomposition of the electrolyte was not capacity at the end of 100 cycles (see Figure 8d). The first cycle
observed during the first lithiation scan with our SiNWs coulombic efficiency (CE) was ∼93%, which is very good for Si-
presumably because of the formation of oxide layer(s) based electrodes and is believed to be due to the presence of
(comprising of SiO, Si2O, and SiO2) upon exposure to air surface oxide(s) that form upon exposure to air.13 The CE
prior to the cell assembly.13 In the second cathodic scan increased rapidly with further cycling to >99%, which was then
(lithiation), a broad hump (between 0.33 and 0.26 V) was maintained up to 100 cycles. SEM images obtained with the
followed by a broad peak at ∼0.2 V and another sharp peak at SiNWs after 100 galvanostatic lithiation/delithiation cycles
∼0.05 V, which correspond to the onset of Li insertion to form indicate that the SiNWs remain in good contact with the current
Li7Si3 and then Li3.16Si. The second anodic scan (delithiation) collector (Figure S6a in the Supporting Information). This
exhibits a peak similar to the first anodic scan, with the humps/ points toward the good integrity of these free-standing SiNW
peaks not showing any notable change thereafter, which is a first (on copper foil) electrodes upon repeated lithiation/delithia-
indication of the stability of the SiNWs upon repeated lithiation/ tion, viz., an aspect of immense significance. Furthermore, the
delithiation. Nyquist plots based on the electrochemical impedance spec-
The potential profiles obtained during galvanostatic lith- troscopy data (EIS), as presented in Figure S6b in the
iation/delithiation of the SiNW-based electrode on the copper Supporting Information, indicate a nearly negligible increment
current collector at current densities equivalent to C/5 and 1C in impedance from the 1st to 100th cycle.
are shown in Figure 8b,c, respectively. At C/5, a first cycle Even at a high current density corresponding to 1C, an
delithiation (i.e., reversible) capacity of 3556 mAh/g was appreciable first cycle reversible capacity of 2462 mAh/g was
17778 [Link]
ACS Appl. Nano Mater. 2022, 5, 17767−17782
ACS Applied Nano Materials [Link] Article

obtained, along with an excellent first cycle coulombic efficiency 4. CONCLUSIONS

of ∼98.3%. Irreversible reactions at the electrode/electrolyte We have successfully demonstrated here the feasibility of
interfaces can get suppressed at high current densities,68 which is growing Si nanowires (SiNWs), having a crystalline Si core and
believed to be the reason for the higher first cycle CE at 1C, as amorphous Si shell, directly on as-received battery-grade copper
compared to that at C/5. In addition to the excellent rate substrates. The hot-wire-assisted VLS mechanism involving the
capability, in terms of a high Li-storage capacity obtained at 1C, dissociation of SiH4 offers a unique advantage for SiNW growth
of further significance is the cyclic stability, which allowed at lower substrate temperatures using Sn as the catalyst,
retentions of ∼89% after 100 cycles and ∼60% after 350 cycles overcoming the challenge associated with the solid solubility
(see Figure 8e), despite the high current density. The superior of Sn in copper. In this regard, the present results demonstrate
cyclic stability at the higher current density (viz., at 1C that while it is indeed not possible to grow SiNW on the oxide-
compared to at C/5) is believed to be partly due to suppression free copper substrate, the presence of native oxide layer(s) on
of the deleterious irreversible reactions at the electrode/ the copper foils acts as a barrier layer that allows the dewetting of
electrolyte interface, which cause capacity fade due to associated Sn nanoparticles, promoting the growth of SiNW via the VLS
stress developments and impedance build-up (see Figure S7b in mechanism.
the Supporting Information).69,70 Further to this, a systematic variation of SiH4 pressure during
3.8. Electrochemical Performance of Free-Standing the SiNW growth process reveals that at low SiH4 pressures (viz.,
SiNW Anodes in Li-Ion “Full” Cell. The as-grown SiNWs on 5 and 10 mTorr), the nanowires get oriented perpendicular to
copper current collector foils were used as the anode in Li-ion the substrate and contain a defect-free crystalline core, along
“full” cell configuration with our home-made nanoscale LiFePO4 with small nanocrystalline regions embedded in the amorphous
(decorating MWCNTs)-based cathode. The details concerning shell. By contrast, at higher SiH4 pressures (viz., 20 and 30
the synthesis, features, and electrochemical behavior of the mTorr), defect substructures, such as twins and stacking faults,
concerned LiFePO4 (decorating MWCNTs) cathode material form in the crystalline core of the SiNWs, with the nanowires no
can be found in our previously published work.13,49 The charge− longer remaining perpendicular to the substrate (rather showing
discharge (voltage) profiles for these “full” cells, within a voltage kinks and bends). Also, no nanocrystalline region was observed
window of 1.2−3.8 V, are shown in Figure 9a, with the in the amorphous shell at the higher SiH4 pressures.
corresponding cyclic stability (i.e., variation of discharge capacity Furthermore, the growth rate increases with the SiH4 pressure
with the cycle number) and coulombic efficiency presented in since more Si radicals are made available, with this increased
Figure 9b. At a current density of 341 μA/cm2 (viz., equivalent growth rate being primarily responsible for the creation of
to 1C), a first cycle discharge capacity of 104 mAh/g was defects in the crystalline core.
obtained for the “full” cell, with an exceptional cyclic stability Variation of the growth duration revealed that the SiNWs
corresponding to the retention of ∼97% capacity at the end of grown for 15 min had a conical shape, but with the nanowires
100 cycles. In the context of the cell capacity, it may be recalled becoming increasingly uniform as the growth duration
here that in the case of a Li-ion “full” cell, the capacity gets increased. With optimization in the growth conditions, SiNWs
limited by the cathode material. These “full” cells were tested in with an aspect ratio of 25 could be obtained. Furthermore,
deep discharge conditions with the lower cell potential reaching different regimes were identified where the crystalline core and
1.2 V and a high charging rate of 1C. The rate capability studies amorphous shell growth are dominant and recessive, respec-
in “half” and “full” cell configurations indicate that >60% of the tively, and vice versa, the understanding of which will be helpful
specific capacities at C/5 get retained even upon the increase in toward fine-tuning SiNW morphology and microstructure to
the current density to 2C (see Figure S7 in the Supporting suit the desired applications (such as solar cells, batteries,
Information). supercapacitors, etc.).
The SiNWs, when used in Li-ion batteries as anodes, sans
The concerned SiNW//LiFePO4 Li-ion “full” cells have been
carbon additive and binder, exhibit a near-theoretical reversible
tested for practical applications, as shown in Figure 9c,d. Figure
Li-storage capacity of ∼3556 mAh/g @ C/5 (with a first cycle
9c shows an array of 61 red LEDs lit up with our cell (marked in a
CE of 93%) and an appreciable capacity of ∼2462 mAh/g at 1C
yellow circle). After discharge, the same “full” cell was charged
rate (with a first cycle CE of >98%), while retaining ∼89% of the
and used for running a consumer electronic device, viz., a capacity after 100 cycles @ 1C. Even in the Li-ion “full” cell with
commercial calculator having a power rating of 0.2 mW and a a home-made LiFePO4-based cathode, a first cycle discharge
voltage rating of 1.5 V, as shown in Figure 9d. A resistor was capacity of ∼104 mAh/g was obtained, along with ∼97%
connected in series with the circuit, and the solar cell available in capacity retention after 100 cycles @ 341 μA/cm2. Thus, we
the calculator was disabled so as to get an accurate result. The have demonstrated here SiNW-based anodes (sans binder and
cell was able to power the calculator seamlessly for an extended carbon additive), with the scale-up potential of large-scale
period. production via HWCVD (invoking the VLS growth mecha-
Considering the scale-up potential of SiNW growth via the nism) and feasibility to tune the SiNW features, as per the need,
concerned technique (viz., HWCVD, invoking a modified VLS toward the development of high-performance next-generation
growth mechanism), with no requirement of a carbon additive Li-ion batteries.

■
and binder for anode preparation (viz., directly grown on the Cu
substrate; contributing to the low irreversible capacity loss), the ASSOCIATED CONTENT
as-developed SiNWs present viable opportunities for the
development of high capacity, rate-capable, and electrochemi-
*
sı Supporting Information
The Supporting Information is available free of charge at
cally stable Li-ion batteries. Furthermore, using the results and
[Link]
associated knowledge base, as disseminated in this paper, the
features of the SiNWs can be tuned to further improve the Section S1: mechanism and methodology of SiNW via the
properties/performances. VLS mechanism using hot-wire CVD; Figure S1:
17779 [Link]
ACS Appl. Nano Mater. 2022, 5, 17767−17782
ACS Applied Nano Materials [Link] Article

schematic representation of the SiNW growth process via S.K.: experimental work for cathode materials development.
the VLS mechanism; Figure S2: XPS spectra revealing the A.M. and R.O.D.: overall idea, regular discussions with co-
O content of copper foils prior to and after acetic acid workers, ideas concerning analysis/interpretations, and correc-
treatment; Figure S3: SEM images of copper foils after tion of the manuscript draft.
acetic acid cleaning and after IPA cleaning; Figure S4: Notes
XRD plots of SiNW growth at different pressures; Figure The authors declare no competing financial interest.

■
S5: cross-sectional SEM images of the SiNWs grown on
copper foil for growth durations; Figure S6: SEM image of
ACKNOWLEDGMENTS
the SiNWs after being subjected to 100 galvanostatic
lithiation/delithiation cycles at a current density equiv- R.O.D. and A.M. would like to thank DST, Govt. of India (vide:
alent to C/5 and Nyquist plots corresponding to EIS of DST/TMD/MES-TS/2k17/24), A.M. would like to thank the
the SiNW-based electrode in the Li “half” cell Swarnajayanti Fellowship Scheme of DST/SERB, Govt. of India
configuration recorded after 1, 10, and 100 discharge (vide: SB/SJF/2021-22/17), for financial supports, IRCC, IIT
cycles; Figure S7: rate capability plots for the SiNW-based Bombay, for financial support, and SAIF and ICCF (IIT
electrodes, in terms of variations of delithiation capacity of Bombay) for enabling the usages of some of the experimental/
the SiNWs (as % of first cycle capacity), in the Li “half” analytical facilities.

■
cell configuration and “full” cell configuration with the
LiFePO4-based cathode (PDF) REFERENCES

■ AUTHOR INFORMATION
Corresponding Authors
(1) Chan, C. K.; Peng, H.; Liu, G.; McIlwrath, K.; Zhang, X. F.;
Huggins, R. A.; Cui, Y. High-Performance Lithium Battery Anodes
Using Silicon Nanowires. Nat. Nanotechnol. 2007, 3, 31−35.
(2) Soam, A.; Kavle, P.; Kumbhar, A.; Dusane, R. O. Performance
Amartya Mukhopadhyay − High Temperature and Energy Enhancement of Micro-Supercapacitor by Coating of Graphene on
Materials Laboratory, Department of Metallurgical Silicon Nanowires at Room Temperature. Curr. Appl. Phys. 2017, 17,
Engineering and Materials Science, Indian Institute of 314−320.
Technology Bombay, Mumbai 400076, India; [Link]/ (3) Li, Q.; Zhu, X.; Xiong, H. D.; Koo, S.-M.; Ioannou, D. E.;
0000-0002-9368-0935; Email: amartya_mukhopadhyay@ Kopanski, J. J.; Suehle, J. S.; Richter, C. A. Silicon Nanowire on Oxide/
[Link] Nitride/Oxide for Memory Application. Nanotechnology 2007, 18,
Rajiv O. Dusane − Semiconductor Thin Films and Plasma No. 235204.
(4) Hochbaum, A. I.; Chen, R.; Delgado, R. D.; Liang, W.; Garnett, E.
Processing Laboratory, Department of Metallurgical
C.; Najarian, M.; Majumdar, A.; Yang, P. Enhanced Thermoelectric
Engineering and Materials Science, Indian Institute of Performance of Rough Silicon Nanowires. Nature 2008, 451, 163−167.
Technology Bombay, Mumbai 400076, India; [Link]/ (5) Shao, M.; Ma, D. D. D.; Lee, S.-T. Silicon Nanowires − Synthesis,
0000-0001-8766-1714; Email: rodusane@[Link] Properties, and Applications. Eur. J. Inorg. Chem. 2010, 2010, 4264−
4278.
Authors (6) Cui, L.-F.; Ruffo, R.; Chan, C. K.; Peng, H.; Cui, Y. Crystalline-
Rashmi Tripathi − Semiconductor Thin Films and Plasma Amorphous Core− Shell Silicon Nanowires for High Capacity and
Processing Laboratory, Department of Metallurgical High Current Battery Electrodes. Nano Lett. 2008, 9, 491−495.
Engineering and Materials Science and High Temperature and (7) Bourderau, S.; Brousse, T.; Schleich, D. M. Amorphous Silicon as a
Energy Materials Laboratory, Department of Metallurgical Possible Anode Material for Li-Ion Batteries. J. Power Sources 1999,
Engineering and Materials Science, Indian Institute of 81−82, 233−236.
Technology Bombay, Mumbai 400076, India; [Link]/ (8) Teki, R.; Datta, M. K.; Krishnan, R.; Parker, T. C.; Lu, T.-M.;
0000-0003-2881-8595 Kumta, P. N.; Koratkar, N. Nanostructured Silicon Anodes for Lithium
Ion Rechargeable Batteries. Small 2009, 5, 2236−2242.
Vaishali Chauhan − Semiconductor Thin Films and Plasma (9) Beaulieu, L. Y.; Eberman, K. W.; Turner, R. L.; Krause, L. J.; Dahn,
Processing Laboratory, Department of Metallurgical J. R. Colossal Reversible Volume Changes in Lithium Alloys.
Engineering and Materials Science, Indian Institute of Electrochem. Solid-State Lett. 2001, 4, A137.
Technology Bombay, Mumbai 400076, India (10) Wang, C.; Ma, Z.; Wang, Y.; Lu, C. Failure Prediction of High-
Pranay Gandharapu − High Temperature and Energy Capacity Electrode Materials in Lithium-Ion Batteries. J. Electrochem.
Materials Laboratory, Department of Metallurgical Soc. 2016, 163, A1157.
Engineering and Materials Science, Indian Institute of (11) Ma, Z. S.; Xie, Z. C.; Wang, Y.; Zhang, P. P.; Pan, Y.; Zhou, Y. C.;
Technology Bombay, Mumbai 400076, India; [Link]/ Lu, C. Failure Modes of Hollow Core−Shell Structural Active Materials
0000-0003-0226-3018 during the Lithiation−Delithiation Process. J. Power Sources 2015, 290,
Sushobhan Kobi − High Temperature and Energy Materials 114−122.
(12) Wang, M.; Ye, H. Microstructure Dependent Chemo-
Laboratory, Department of Metallurgical Engineering and Mechanical Behavior of Amorphous Si Anodes for Li-Ion Batteries
Materials Science, Indian Institute of Technology Bombay, upon Delithiation. J. Power Sources 2022, 520, No. 230803.
Mumbai 400076, India (13) Jangid, M. K.; Sinha, S.; Lakhnot, A. S.; Sonia, F. J.; Kumar, A.;
Complete contact information is available at: Dusane, R. O.; Mukhopadhyay, A. Effect of the Presence of Si-Oxide/
[Link] Sub-Oxide Surface Layer(s) on ‘Micron-Sized’ Si Wires towards the
Electrochemical Behavior as Anode Material for Li-Ion Battery.
Electrochim. Acta 2019, 297, 381−391.
Author Contributions (14) Nadimpalli, S. P. V.; Sethuraman, V. A.; Dalavi, S.; Lucht, B.;
R.T.: most of the materials development, experimental work, Chon, M. J.; Shenoy, V. B.; Guduru, P. R. Quantifying Capacity Loss
analysis, and write-up. V.C.: experimental work for SiNW Due to Solid-Electrolyte-Interphase Layer Formation on Silicon
materials development. P.G.: assistance with electrochemical Negative Electrodes in Lithium-Ion Batteries. J. Power Sources 2012,
experimental work, discussions during analysis, and write-up. 215, 145−151.

17780 [Link]
ACS Appl. Nano Mater. 2022, 5, 17767−17782
ACS Applied Nano Materials [Link] Article

(15) Paloukis, F.; Elmasides, C.; Farmakis, F.; Selinis, P.; Neophytides, (35) Schmidt, V.; Wittemann, J. V.; Senz, S.; Gösele, U. Silicon
S. G.; Georgoulas, N. Electrochemical Impedance Spectroscopy Study Nanowires: A Review on Aspects of Their Growth and Their Electrical
in Micro-Grain Structured Amorphous Silicon Anodes for Lithium-Ion Properties. Adv. Mater. 2009, 21, 2681−2702.
Batteries. J. Power Sources 2016, 331, 285−292. (36) Schmidt, V.; Wittemann, J. V.; Gosele, U. Growth, Thermody-
(16) Jangid, M. K.; Sonia, F. J.; Aslam, M.; Mukhopadhyay, A. Lower namics, and Electrical Properties of Silicon Nanowires. Chem. Rev.
Limit to Si-Dimension for Retaining Graphenic Carbon Based 2010, 110, 361−388.
‘Buffer’Effective towards Bestowing Si-Electrodes with Cyclic Stability. (37) Soam, A.; Dusane, R. Controlling the Size of Interior Core of
Carbon 2020, 165, 428−433. Silicon Nanowires. J. Nano Res. 2017, 45, 193−198.
(17) Datta, M. K.; Maranchi, J.; Chung, S. J.; Epur, R.; Kadakia, K.; (38) Meshram, N. P.; Kumbhar, A.; Dusane, R. O. Silicon Nanowire
Jampani, P.; Kumta, P. N. Amorphous Silicon−Carbon Based Nano- Growth on Glass Substrates Using Hot Wire Chemical Vapor
Scale Thin Film Anode Materials for Lithium Ion Batteries. Electrochim. Deposition. Thin Solid Films 2011, 519, 4609−4612.
Acta 2011, 56, 4717−4723. (39) Meshram, N.; Kumbhar, A.; Dusane, R. O. Synthesis of Silicon
(18) Li, S.; Niu, J.; Zhao, Y. C.; So, K. P.; Wang, C.; Wang, C. A.; Li, J. Nanowires Using Tin Catalyst by Hot Wire Chemical Vapor
High-Rate Aluminium Yolk-Shell Nanoparticle Anode for Li-Ion Processing. Mater. Res. Bull. 2013, 48, 2254−2258.
Battery with Long Cycle Life and Ultrahigh Capacity. Nat. Commun. (40) Wu, H.; Cui, Y. Designing Nanostructured Si Anodes for High
2015, 6, 7872. Energy Lithium Ion Batteries. Nano Today 2012, 7, 414−429.
(19) Huang, G.; Han, J.; Lu, Z.; Wei, D.; Kashani, H.; Watanabe, K.; (41) Singh, B. K.; Shaikh, A.; Dusane, R. O.; Parida, S. Copper Oxide
Chen, M. Ultrastable Silicon Anode by Three-Dimensional Nano- Nanosheets and Nanowires Grown by One-Step Linear Sweep
architecture Design. ACS Nano 2020, 14, 4374−4382. Voltammetry for Supercapacitor Application. J. Energy Storage 2020,
(20) Ashuri, M.; He, Q.; Shaw, L. L. Silicon as a Potential Anode 31, No. 101631.
Material for Li-Ion Batteries: Where Size Geometry and Structure (42) Van Dat, P.; Viet, N. X. Facile Synthesis of Novel Areca Flower
Matter. Nanoscale 2016, 8, 74−103. like Cu2O Nanowire on Copper Foil for a Highly Sensitive Enzyme-
(21) Wei, C. Y.; Sun, Y. T.; Liu, Y. L.; Liu, T. R.; Wen, C. Y.; Wen, C. Free Glucose Sensor. Mater. Sci. Eng., C 2019, 103, No. 109758.
Y.; Wen, C. Y. Lithiation-Induced Fracture of Silicon Nanowires (43) Lu, L.-L.; Ge, J.; Yang, J.-N.; Chen, S.-M.; Yao, H.-B.; Zhou, F.;
Observed by in-Situ Scanning Electron Microscopy. Nanotechnology Yu, S.-H. Free-Standing Copper Nanowire Network Current Collector
for Improving Lithium Anode Performance. Nano Lett. 2016, 16,
2020, 31, 364001.
(22) Xu, W.; Vegunta, S. S. S.; Flake, J. C. Surface-Modified Silicon 4431−4437.
(44) Mishra, D.; Jangid, M. K.; Chhangani, S.; Gandharapu, P.; Prasad,
Nanowire Anodes for Lithium-Ion Batteries. J. Power Sources 2011, 196,
M. J. N. V.; Mukhopadhyay, A. Lattice Distortion of Current Collector
8583−8589.
upon Supporting Dimensional Changes of Electrode-Active Materials
(23) Misra, S.; Liu, N.; Nelson, J.; Hong, S. S.; Cui, Y.; Toney, M. F. In
in Alkali-Metal-Ion Batteries. Energy Fuels 2020, 34, 7763−7769.
Situ X-Ray Diffraction Studies of (De)Lithiation Mechanism in Silicon
(45) Motayed, A.; Bonevich, J. E.; Krylyuk, S.; Davydov, A. V.; Aluri,
Nanowire Anodes. ACS Nano 2012, 6, 5465−5473.
G.; Rao, M. V. Correlation between the Performance and Micro-
(24) Ruffo, R.; Hong, S. S.; Chan, C. K.; Huggins, R. A.; Cui, Y.
structure of Ti/Al/Ti/Au Ohmic Contacts to p-Type Silicon
Impedance Analysis of Silicon Nanowire Lithium Ion Battery Anodes. J.
Nanowires. Nanotechnology 2011, 22, 75206.
Phys. Chem. C 2009, 113, 11390−11398. (46) Chavez, K. L.; Hess, D. W. A Novel Method of Etching Copper
(25) McDowell, M. T.; Lee, S. W.; Nix, W. D.; Cui, Y. 25th
Oxide Using Acetic Acid. J. Electrochem. Soc. 2001, 148, G640−G643.
Anniversary Article: Understanding the Lithiation of Silicon and Other (47) Soam, A.; Arya, N.; Meshram, N.; Kumbhar, A.; Dusane, R.
Alloying Anodes for Lithium-ion Batteries. Adv. Mater. 2013, 25, Formation of Sn Nano-Template by Hot-Wire Chemical Vapor Process
4966−4985. on Different Substrates. Surf. Interfaces 2017, 8, 193−198.
(26) Chen, L. B.; Xie, J. Y.; Yu, H. C.; Wang, T. H. An Amorphous Si (48) Soam, A.; Arya, N.; Dusane, R. A Detailed Study on the Growth
Thin Film Anode with High Capacity and Long Cycling Life for of Silicon Nanowires by Hot Wire Chemical Vapor Process: Concept of
Lithium Ion Batteries. J. Appl. Electrochem. 2009, 39, 1157−1162. Critical Size of Sn Catalyst. J. Nanopart. Res. 2020, 22, 363.
(27) Obrovac, M. N.; Krause, L. J. Reversible Cycling of Crystalline (49) Satam, M. K.; Natarajan, R.; Kobi, S.; Jangid, M. K.; Krishnan, Y.;
Silicon Powder. J. Electrochem. Soc. 2007, 154, A103. Mukhopadhyay, A. Nucleation-Growth Induced Phase Transformation
(28) Le Comber, P. G.; Madan, A.; Spear, W. E. Electronic Transport during Delithiation/Lithiation of ‘Ultra-Small’ LiFePO4 Nanoparticles
and State Distribution in Amorphous Si Films. J. Non-Cryst. Solids 1972, Decorating Carbon Nanotubes. Scr. Mater. 2016, 124, 1−5.
11, 219−234. (50) He, L.; Liu, Y. W.; Tong, W. J.; Lin, J. G.; Wang, X. F. Surface
(29) Little, T. W.; Takahara, K.; Koike, H.; Nakazawa, T.; Yudasaka, Energy Engineering of Cu Surface by Strain: First-Principles
I.; Ohshima, H. Low Temperature Poly-Si TFTs Using Solid Phase Calculations. Surf. Rev. Lett. 2013, 20, 1350054.
Crystallization of Very Thin Films and an Electron Cyclotron (51) Mishra, A. K.; Roldan, A.; de Leeuw, N. H. CuO Surfaces and
Resonance Chemical Vapor Deposition Gate Insulator. Jpn. J. Appl. CO2 Activation: A Dispersion-Corrected DFT+U Study. J. Phys. Chem.
Phys. 1991, 30, 3724. C 2016, 120, 2198−2214.
(30) Soam, A.; Meshram, N.; Arya, N.; Kumbhar, A.; Dusane, R. (52) Rathi, S. J.; Jariwala, B. N.; Beach, J. D.; Stradins, P.; Taylor, P. C.;
Controlling the Geometrical Orientation of Hot-Wire Chemical Vapor Weng, X.; Ke, Y.; Redwing, J. M.; Agarwal, S.; Collins, R. T. Tin-
Process Grown Silicon Nanowires. Thin Solid Films 2017, 635, 58−62. Catalyzed Plasma-Assisted Growth of Silicon Nanowires. J. Phys. Chem.
(31) Soam, A.; Arya, N.; Kumbhar, A.; Dusane, R. Controlling the C 2011, 115, 3833−3839.
Shell Microstructure in a Low-Temperature-Grown SiNWs and (53) Wynblatt, P.; Gjostein, N. A. Particle Growth in Model
Correlating It to the Performance of the SiNWs-Based Micro- Supported Metal CatalystsI. Theory. Acta Metall. 1976, 24, 1165−
Supercapacitor. Appl. Nanosci. 2016, 6, 1159−1165. 1174.
(32) Jangid, M. K.; Lakhnot, A. S.; Vemulapally, A.; Sonia, F. J.; Sinha, (54) Tang, J.; Maurice, J.-L.; Chen, W.; Misra, S.; Foldyna, M.;
S.; Dusane, R. O.; Mukhopadhyay, A. Crystalline Core/Amorphous Johnson, E. V.; i Cabarrocas, P. R. Plasma-Assisted Growth of Silicon
Shell Structured Silicon Nanowires Offer Size and Structure Dependent Nanowires by Sn Catalyst: Step-by-Step Observation. Nanoscale Res.
Reversible Na-Storage. J. Mater. Chem. A 2018, 6, 3422−3434. Lett. 2016, 11, 455.
(33) Gale, W. F.; Totemeier, T. [Link] Metals Reference Book; (55) Baker, H.; Okamoto, [Link] Handbook. Alloy Phase Diagrams.
Elsevier Ltd, 2003, p 14−19. Vol. 3, 1992, p 501.
(34) Wagner, R. S.; Ellis, W. C. Vapor-liquid-solid Mechanism of (56) Baheti, V. A.; Kashyap, S.; Kumar, P.; Chattopadhyay, K.; Paul, A.
Single Crystal Growth. Appl. Phys. Lett. 1964, 4, 89−90. Solid−State Diffusion−Controlled Growth of the Intermediate Phases

17781 [Link]
ACS Appl. Nano Mater. 2022, 5, 17767−17782
ACS Applied Nano Materials [Link] Article

from Room Temperature to an Elevated Temperature in the Cu−Sn

and the Ni−Sn Systems. J. Alloys Compd. 2017, 727, 832−840.
(57) Gandharapu, P.; Suman, A.; Jangid, M. K.; Velaga, S.; Poswal, H.
K.; Mukhopadhyay, A. Operando Investigations toward Changeover of
Phase Assemblage and Associated Electrochemical Behavior during
Lithiation/Delithiation Cycles of Sn-Based Intermetallic Electrodes.
ACS Appl. Energy Mater. 2020, 3, 11249−11259.
(58) Liu, B.; Tian, Y.; Wang, C.; An, R.; Liu, Y. Extremely Fast
Formation of CuSn Intermetallic Compounds in Cu/Sn/Cu System via
a Micro-Resistance Spot Welding Process. J. Alloys Compd. 2016, 687,
667−673.
(59) Ball, J.; Bowen, L.; Mendis, B. G.; Reehal, H. S. Low Pressure
Plasma Assisted Silicon Nanowire Growth from Self Organised Tin
Catalyst Particles. CrystEngComm 2013, 15, 3808−3815.
(60) Smith, J. E., Jr.; Brodsky, M. H.; Crowder, B. L.; Nathan, M. I.;
Pinczuk, A. Raman Spectra of Amorphous Si and Related Tetrahedrally
Bonded Semiconductors. Phys. Rev. Lett. 1971, 26, 642.
(61) Kravets, V. G.; Kolmykova, V. Y. Raman Scattering of Light in
Silicon Nanostructures: First-and Second-Order Spectra. Opt. Spectrosc.
2005, 99, 68−73.
(62) i Cabarrocas, P. R.; Cariou, R.; Labrune, M. Low Temperature
Plasma Deposition of Silicon Thin Films: From Amorphous to
Crystalline. J. Non-Cryst. Solids 2012, 358, 2000−2003.
(63) Dusane, R. O.; Dusane, S. R.; Bhide, V. G.; Kshirsagar, S. T.
Hydrogenated Microcrystalline Silicon Films Produced at Low
Temperature by the Hot Wire Deposition Method. Appl. Phys. Lett.
1993, 63, 2201−2203.
(64) Westwater, J.; Gosain, D. P.; Tomiya, S.; Usui, S.; Ruda, H.
Growth of Silicon Nanowires via Gold/Silane Vapor−Liquid−Solid
Reaction. J. Vac. Sci. Technol., B: Microelectron. Nanometer Struct.−Pro-
cess., Meas., Phenom. 1997, 15, 554−557.
(65) Matsumura, H.; Umemoto, H.; Gleason, K. K.; Schropp, R. E.
[Link] Chemical Vapor Deposition; Wiley Online Library, 2019, p
19−20.
(66) Ohring, [Link] Science of Thin Films. Academic Press
London ,1995, p 97.
(67) Reyes Jiménez, A.; Klöpsch, R.; Wagner, R.; Rodehorst, U. C.;
Kolek, M.; Nölle, R.; Winter, M.; Placke, T. A Step toward High-Energy
Silicon-Based Thin Film Lithium Ion Batteries. ACS Nano 2017, 11,
4731−4744.
(68) Sonia, F. J.; Jangid, M. K.; Ananthoju, B.; Aslam, M.; Johari, P.;
Mukhopadhyay, A. Understanding the Li-Storage in Few Layers
Graphene with Respect to Bulk Graphite: Experimental, Analytical and
Computational Study. J. Mater. Chem. A 2017, 5, 8662−8679.
(69) Jangid, M. K.; Mukhopadhyay, A. Real-Time Monitoring of
Stress Development during Electrochemical Cycling of Electrode
Materials for Li-Ion Batteries: Overview and Perspectives. J. Mater.
Chem. A 2019, 7, 23679−23726.
(70) Jangid, M. K.; Sonia, F. J.; Kali, R.; Ananthoju, B.;
Mukhopadhyay, A. Insights into the Effects of Multi-Layered Graphene
as Buffer/Interlayer for a-Si during Lithiation/Delithiation. Carbon
2017, 111, 602−616.

17782 [Link]
ACS Appl. Nano Mater. 2022, 5, 17767−17782