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a
School of Materials Science and Nanotechnology, Jadavpur University, Kolkata 700032
c
Thin film and Nano Science Laboratory, Department of Physics, Jadavpur University, Kolkata
700032
* E-mail: shrabani.ghosh2012@gmail.com
Abstract:
Terahertz is an important but underutilized frequency range which lies between 0.3 THz to 10
THz in electromagnetic spectrum occupying middle ground and properties of both microwave
and infrared region. As conventional electronic devices have failed to generate and detect the
terahertz wave, there is a high demand to find alternatives. Silicon nanowire is still under
research as a terahertz emitter. Here, grass like silicon nanowires are synthesized by two stage
metal assisted chemical etching (MaCE) process varying different parameters like temperature,
HF treatment and carbon catalyst for p type silicon wafer (100). With varying conditions, the
length and diameter of the nanowires are changed. Without HF treatment, silicon nanowires
(SiNW) contain superficial silicon oxide layer which changes the properties accordingly in
comparison with HF treated SiNW (SiNW-HF). As temperature increases, HF etching rate has
been enhanced resulting in highly dense more fine nanowires in the same area (SiNW-HF-T). By
providing conductive back made of carbon, the etching rate of silicon wafer is enhanced in a
nanowires with average length of 1.6 m, 3 m, and 7 m, 14.4 m, respectively. To investigate
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their surface roughness properties with varying synthesis process, wettability study is performed
in which nature of the nanowires has high impact. As terahertz detector, silicon nanowires have
Deposition of RGO on silicon nanowires enhances the roughness to an extent that hydrophilic
nature of the film is converted to hydrophobic for SiNW-HF-T/RGO(s). This material can be
Introduction:
Progress of science and technology has inspired the researchers to utilize the terahertz (THz)
frequency gap in electromagnetic (EM) spectrum properly. It lies in between 0.3 THz to 10 THz
in electromagnetic spectrum occupying middle ground of microwave and infrared region[1, 2]. It
contains some properties of the both wavelengths. Like all other waves, it can also create
pictures and transmit information [2]. As a part of EM wave, the properties of THz are calculated
employing Maxwell Equation [2, 3]. Generally, conventional electronic devices are inappropriate
for generation and coherent detection of terahertz frequency with wavelength from 30 m to 3
mm, though it has vast application in industry for product inspection, investigation of defects in
tablet coating, spectroscopy, screening etc., even detection of cancer can be done by this EM
wave[1, 4, 5]. Researchers are now paying their attention to the investigation of such materials
In nanotechnology, one dimensional nanostructures like nanowire, nanobelts etc are essential
building blocks for electronic devices in present and upcoming technology. Nanowire is quasi
1D nanostructure with diameter less than 300 nm and length to diameter aspect ratio should be
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more than ten[6]. It has several advantages like enhanced strain relaxation [7], cheap with respect
to cost and material consumption, high surface area to volume ratio and efficient light trapping
[8, 9]. Such unique properties are responsible for its applications in solar cells [10], photo
detector [11], single photon source [12], transistor [13] nanoscale lasers [14] etc. Furthermore,
this 1D structure can give new insight towards shape and size effect on different properties [15].
(THz) radiator. It is primarily due to the combined oscillations of conductive electrons and
confinement at the surface of nanostructures resulting in localized surface plasmon (LSP) effect
[16, 17].
As per previous report of Seletskiy et al., the enhanced emission of THz radiation is observed
from free-standing InAs nanowires (NWs) [16]. The high-efficiency dipole radiation
perpendicular to the NW length is attributed for such efficiency having its surface parallel to the
direction of charge transport. The nanosize ZnSe grains can give impressive THz emission from
the surface of as reported by He et al. due to local field enhancement effect [18]. There is another
report on THz emission from InP membranes [17]. Additionally, Gyeong Bok Jung et al. has
synthesized n type silicon nanowires by metal assisted chemical etching and studied how the
Now, two dimensional sheets like structure (2D) are enriched by its own unique properties. In
well known for its broad-band photo detection property from visible to infrared range [21]. As
obtained from theoretical explanation, bandgap variation of graphene can extend its working
spectrum to far infrared (FIR) region, even at terahertz range (THz) [22, 23]. From the previous
studies it is observed that reduced graphene oxide (RGO) extracted from graphite by chemical
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exfoliation pursues a natural energy gap [24]. The narrow energy gap property of RGO is
appropriate as photodetector from mid-infrared (MIR) (2.5–30 μm) to even THz (30–3000 μm)
range. As per previous reports of Chitara et al., the NIR (1.55 μm) photodetectors can be
achieved employing extensively reduced RGO [25]. There are few limitations of RGO to behave
as broadband photo detector as limited optical absorbance, energy gap of tens of meV which are
However, apart from emission of THz frequency from Si nanowire (SiNW) arrays, they have few
advantages as photo detector also which can compensate the deficiencies present in RGO. Si has
bandgap of ∼1.12 eV, appropriate for photodetection from the VIS to NIR range. Additionally,
the vertically grown nanowire array can decrease light reflection intensively over a wide spectral
range from VIS to NIR. As a result, light harvesting property of SiNW array is significantly
improved. Thus, the hybrid composed of SiNW arrays and RGO can enhance the light harvesting
witnessed from THz to VIS, even at NIR range [26]. Cao et al. has introduced RGO and SiNW
arrays into a single photodetector heterojunction which has broad photo response from visible to
Keeping all these properties in mind, silicon nanowires are synthesized here in MaCE [28]
process varying( with variation of)different synthesis parameters to obtain different lengths
which have high impact on terahertz emission. RGO and silicon nanowire hybrid system is
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Experimental Section:
Synthesis:
Silicon nanowires are synthesized by conventional two step metal assisted chemical etching
(MACE) process employing commercially available p type silicon wafers (100). Few parameters
are optimized to synthesis wire like silicon in nano range. In the first step, silicon wafers are
cleaned by sonication in ethanol and acetone. After that, wafers are immersed in piranha solution
to remove organic residues. A layer of oxygen is produced by piranha solution which is removed
by 5% HF solution. After every step, wafers are rinsed by deionized water (DI). The cleaned
wafers are transferred into HF/AgNO3 solution for one minute to deposit silver nanoparticles on
the surface. After rinsing, the Si wafers are etched by HF/H 2O2 solution for 60 minutes.
Thereafter, the wafers are dipped into HNO3 to dissolve excess Ag nanoparticles. Thus, silicon
nanowires are produced but a thin oxide layer is also generated by HNO 3 which is removed by
HF solution, again. In this paper, different parameters are varied during this synthesis process.
Two different sets of silicon nanowires are produced with and without the last HF treatment
which are termed as SiNW-HF and SiNW, respectively. To investigate the effect of temperature
on synthesis, one set of sample is etched at 60C naming SiNW-HF-T. Additionally, another set
Graphene oxide (GO) is synthesized from graphite powder by modified Hummer’s method. Half
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SiNW-HF-T/RGO(s):
The hydrothermally produced RGO is sonicated in ethanol and spin coated on SiNW-HF-T
forming SiNW-HF-T/RGO(s).
SiNW-HF-T/RGO(h):
Here, the remaining half of synthesized GO is sonicated in DI water for quick dispersion and the
solution is transferred into a stainless steel Teflon line autoclave. The SiNW-HF-T is tied in a
glass slide keeping etched side bare and front faced and the glass slide is placed inside the
autoclave in an inclined manner keeping upside downward. The whole system is kept at 180C
Characterizations:
Morphological study as synthesized samples are conducted by field emission scanning electron
microscopy (FESEM, Hitachi, S-4800). RAMAN analysis is conducted with the excitation of a
532 nm laser source (WITECH) which can assure the RGO layer formation. To investigate the
surface property of nanowires and composites wettability study is performed using Dataphysics
OCA 15EC.
Morphological Analysis:
1(a) represents the FESEM image of SiNW confirming the formation of nanowires which are
little agglomerated. As the HF treatment is not performed, SiO2 is not removed from the surface
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of SiNW. Besides, the distinct nanowires are observed in SiNW-HF as shown in figure 1(b).
Here, the oxide layer originated from nitric acid is washed out by HF acid.
Figure 1: FESEM image (top view) of (a) SiNW, (b) SiNW-HF (c) SiNW-HF-T (d)
SiNW-HF/C
1(c) is the top view FESEM of SiNW-HF-T assuring the perfect formation of nanowires even at
high temperature. Carbon catalyst has been used in SiNW-HF/C where carbon tape is fixed at the
back side of silicon wafer to examine the activity of carbon as etching catalyst. The perfect
Figure 2 is the cross-sectional FESEM image of silicon nanowires varying different synthesis
parameters. SiNW has the length of 500 nm to 2 m as shown in figure 2(a) whereas SiNW-HF
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consists of distinct nanowires with length of 2 to 3m with more sharpness. Here, HF treatment
plays an important role to consider the change in morphology. Figure2(c) is the cross sectional
view of SiNW-HF-T containing longer nanowires than previous two methods with the length of
7 to 10 m. Such enlargement of nanowire is the outcome of high temperature etching process.
Temperature eases the oxidation below the silver nanoparticles during synthesis which results in
higher rate of etching by HF at 60C. As the HF/H2O2 etching rate rises, wafer can be etched
Figure 2: FESEM image (cross section) of (a) SiNW, (b) SiNW-HF (c) SiNW-HF-T (d),
(e) SiNW-HF/C
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Additionally, SiNW-HF/C is displayed in figure 2(d) and (e) in different magnifications which
depict the most perfect and homogeneous formation of nanowires with the length of almost 14 to
14.5 m. Another synthesis parameter, carbon catalyst is important here to speed up the HF/H 2O2
etching in a more directional way in room temperature without changing itself. It results in most
directionally vertical and systematic formation of nanowires with highest length among all the
as-synthesized nanowires. Now, another parameter which can be analyzed from FESEM is
diameter of the nanowires in different conditions. For high temperature etching process, SiNW-
HF-T has narrower diameter than other samples. The diameter of nanowire for
Figure 3: FESEM image of (a) hydrothermally synthesized RGO (12h), (b) SiNW-HF-
SiNW-HF-T/RGO(h) hybrid
SiNW-HF/C is quite wider and similar (constant)as we progress from tip to base which is not the
property of other nanowires. SiNW, SiNW-HF and SiNW-HF-T have narrow tip and wide base
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of nanowires. Carbon tape catalyzes the etching reaction in a most directive way which causes
the straight formation of homogenous nanowires like physical method in SiNW-HF/C. In the
second step, RGO is deposited on HF treated silicon nanowires etched at room temperature.
Here, two different synthesis processes have been followed. Figure 3(a) is the FESEM image of
hydrothermally synthesized RGO which is thin and very fine in nature. This RGO is spin coated
on SiNW-HF –T which is shown in figure 3(b). A successful deposition of fine RGO sheet just
hydrothermally (6h) in presence of silicon nanowires so that GO can be reduced and deposited
on nanowires, simultaneously. Figure 3(c) depicts the FESEM image of RGO deposited on
SiNW-HF-T in high magnification. Here, RGO sheet is thicker than previous process. The top
view FESEM of SiNW-HF-T/RGO(h) is represented in figure 3(d). It shows that RGO sheet is
deposited on silicon nanowires lengthwise. The nanowires are fully covered by thick layer of
RGO sheet, thus distinct nature of nanowires are modified by joining each other through the
dense 2D sheet.
RAMAN Analysis:
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Primarily, RAMAN spectroscopy is conducted to confirm the formation of RGO in the hybrid
figure 4(a) and (b), respectively. There are Raman active peak at 526 and 528 cm -1 for both the
hybrid system and they are mainly first order transverse optical (TO) phonon mode of the silicon
nanowires [29]. Thus, presence of silicon nanowires can be reassured from the RAMAN
spectroscopy. Besides, the RAMAN peak situated at 1361 and 1353 cm -1 for both the hybrid
correspond to D band (ID) of graphene which arises due to the presence of defects like
corrugation, twisting and edges. Another intense peak at 1602 and 1603 cm -1 of both figures in
figure 4 are associated to G band (IG) of graphene which are the contribution of doubly
degenerate E2g phonon modes at the Brillouin zone of the sp2 hybridized carbon network of
graphite. The ratio of the intensity of ID and IG (ID/IG) denotes the average size of sp2 domain. For
smaller size of sp2 domain, higher ratio is achieved [30]. This property is observed in RGO for
its enhanced aromaticity and delocalization of network. During chemical reduction sp 3 gets
diminished while the conjugated graphene network of sp2 carbon atoms is re-established.
Generally, the size of the re-established network is smaller than the graphite layer which causes
the increment of ratio ID/IG. For SiNW-HF-T/RGO(s), the ratio is 1.1 whereas for SiNW-HF-
T/RGO(h) it is 1.2. This indicates more number of defects in the hydrothermally synthesized
hybrid system. Two small and broad peaks are observed within 2680 to 2940 cm -1 which are
assigned to the D peak and defect activated D+D peak, respectively. The number and coupling
between the layers of graphene are correlated with the position and the shape of 2D band [31].
Here, intensity of 2D peak is weak for both types of chemical synthesis processes though the
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Figure 5: DI
Wettability contact angle on (a) Si wafer; (b),(c) SiNW; (d),(e) SiNW-HF; (f),(g) SiNW-
study:
HF-T; (h),(i) SiNW-HF/C; (j) SiNW-HF-T/RGO(s); (k) SiNW-HF-T/RGO(h)
Wettability Study:
observed from figure 5(a), Si wafer pursues DI contact angle (CA) of 76.1 which depicts that
the wafer is hydrophilic in nature. Figure 5(b) is DI CA on SiNW when the drop touches the
surface and it is 40 denoting hydrophilic surface property. Though, the droplet starts to spread
out after that and the CA becomes 12 after ten minutes (after stability). It can be assumed that
of oxide layer is prominent here which increases the surface energy of the subsptrate resulting in
wettability study. Wenzel model can be applied for SiNW which transforms the surface more
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hydrophilic than smooth wafer. It correlates with the high surface roughness property of SiNW
[32].
After that, wettability is conducted for SiNW-HF which is presented in figure 5(d) and (e). It
describes the opposite surface property of SiNW. The initial CA is 130.5 denoting the
hydrophobicity and even after stability, it maintains the angle to be 123.3 which is quite stable.
After removal of oxide layer by HF treatment, there is a drastic change in surface property. The
surface energy is reduced here. Additionally, air trapping which prohibit the water spreading has
been occurred within nanowires. However, the surface roughness can be described by Cassie-
nanowires[33].
The DI CAs on SiNW-HF-T are presented in figure 5(f) and (g). The initial CA is 92.17and
after stability test, it becomes 5. The water droplet diminishes after certain time describing
superhydrophilic property. However, initial CA is hydrophobic in nature but due to the high
length and lowest diameter of nanowires, pining effect on DI droplet becomes prominent easing
the spread of water. Thus, morphology is an important factor for fluctuating surface property.
The CAs on SiNW-HF/C are represented in figure 5(h) and (i) which describe that the surface is
hydrophobic in nature with CA of 110 but after certain time (ten minutes), the angle transforms
to 71.73 which denotes hydrophilicity. Thus, a typical surface roughness property is observed
treated nanowires pursue high CA with hydrophobic property as observed from SiNW-HF. Here,
the extremely high length becomes the obstacle to hold the water droplet. Again, the CA is
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higher for SiNW-HF/C than SiNW-HF-T due to its wide diameter, the surface pinning of
Figure 5(j) and (k) describes the wettability property of SiNW-HF-T/RGO(s) and SiNW-HF-
symbolizing highly hydrophobic surface with high stability. Thus, the pinning effect of SiNW-
HF-T is overcome using spin coated RGO sheet. The surface roughness property can be
hydrophobic. Here, due to hydrothermal reduction of RGO, the surface becomes so uneven that
Silicon nanowires can be employed as THz emitter. As obtained from previous literature, n type
silicon nanowires can behave as efficient THz emitter which is length dependent. Considering
the length and diameter of nanowire as important factors, several synthesis parameters are varied
to obtain different lengths of nanowires. They can be utilized in THz radiation system according
to its suitable applications. Additionally, silicon nanowire MOSFET (SNFET) has a great future
in THz integrated circuit application [13, 35]. SiNW-HF-T/RGO hybrid can be employed as
broadband photodetector from visible to even THz frequency by varying the bandgap of RGO
deposited on nanowire.
Conclusion:
It can be concluded that silicon nanowires are successfully synthesized by MACE process in
different condition. Long nanowires are obtained at high temperature etching process with
sharpest tip. Using carbon tape as catalyst high nanowires are achieved with wider diameter than
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(with respect to) other nanowires. Furthermore, HF treatment on nanowires is also an important
parameter to discuss. It influences the surface energy and roughness properties which have high
impact on wettability. However, long nanowires have adverse effect in holding water droplet on
tip which transforms the surface to superhyrophilic in nature. Though, longest nanowires with
wide diameter as observed in SiNW-HF/C have both wetting properties with time. Using two
properties have been analyzed. SiNW-HF-T/RGO(s) has highly hydrophobic surface whereas
SiNW-HF-T/RGO (h) is just hydrophobic in nature with high stability with time. Silicon
nanowires and its hybrid with RGO can be accomplished as efficient terahertz emitter and broad
band photo detector, respectively. It has huge application in imaging, remote sensing, photometer
Acknowledgements:
One of us (SG) wishes to thank the Council for Scientific and Industrial Research (CSIR), the
Government of India, for providing her a senior research fellowship through ‘CSIR-SRF’ (File
no: 09/096(0926)/2018-EMR-I) while other (AC) wants to thank TEQIP phase II scheme,
Jadavpur University for providing fellowship during the work. The authors wish to acknowledge
the University Grants Commission (UGC), the Govt. of India for the support under the
“University with Potential for Excellence (UPE-II)” scheme. The authors want to thank
References:
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[2] X.-C. Zhang and J. Xu, Introduction to THz wave photonics vol. 29: Springer, 2010.
[3] Y.-S. Lee, Principles of terahertz science and technology vol. 170: Springer Science &
[4] T. Shibuya and K. Kawase, "Terahertz applications in tomographic imaging and material
[5] K. Peng, P. Parkinson, L. Fu, Q. Gao, N. Jiang, Y.-N. Guo, et al., "Single nanowire
photoconductive terahertz detectors," Nano letters, vol. 15, pp. 206-210, 2015.
[6] H. J. Joyce, J. L. Boland, C. L. Davies, S. A. Baig, and M. B. Johnston, "A review of the
2016.
arrays for photovoltaic applications," Nature materials, vol. 9, pp. 239-244, 2010.
16 | P a g e
[10] M. Yao, S. Cong, S. Arab, N. Huang, M. L. Povinelli, S. B. Cronin, et al., "Tandem solar
cells using GaAs nanowires on Si: design, fabrication, and observation of voltage
[13] Y. Chen, J. He, Y. Wang, X. Lin, L. Zhang, and M. Chan, "Terahertz Wave Generation
"Ultrafast plasmonic nanowire lasers near the surface plasmon frequency," Nature
nanowire superlattice structures for nanoscale photonics and electronics," Nature, vol.
Moewe, et al., "Observation of THz emission from InAs nanowires," pp. 1-2.
terahertz emission from porous InP (111) membranes," Applied Physics Letters, vol. 86,
p. 021904, 2005.
17 | P a g e
[18] S. He, X. Chen, X. Wu, G. Wang, and F. Zhao, "Enhanced terahertz emission from ZnSe
nano-grain surface," Journal of lightwave technology, vol. 26, pp. 1519-1523, 2008.
dependent terahertz emission of silicon nanowires," Optics Express, vol. 18, pp. 16353-
16359, 2010.
[20] R. Cheng, Y. Zhou, H. Liu, J. Liu, G. Sun, X. Zhou, et al., "Tunable graphene-based
terahertz absorber via an external magnetic field," Optical Materials Express, vol. 10, pp.
501-512, 2020.
"Fine structure constant defines visual transparency of graphene," Science, vol. 320, pp.
1308-1308, 2008.
phototransistor: Proposal and analysis," Japanese Journal of Applied Physics, vol. 48, p.
04C144, 2009.
[23] V. Ryzhii, V. Mitin, M. Ryzhii, N. Ryabova, and T. Otsuji, "Device model for graphene
transition in graphene oxide," The Journal of Physical Chemistry C, vol. 113, pp. 15768-
15771, 2009.
18 | P a g e
[26] K. Peng, Y. Xu, Y. Wu, Y. Yan, S. T. Lee, and J. Zhu, "Aligned single‐crystalline Si
nanowire arrays for photovoltaic applications," small, vol. 1, pp. 1062-1067, 2005.
[27] Y. Cao, J. Zhu, J. Xu, J. He, J. L. Sun, Y. Wang, et al., "Ultra‐broadband photodetector
Metal Assisted Chemically Etched (MaCE) Grass Like Silicon Nanowires," pp. 213-217.
[29] R.-p. Wang, G.-w. Zhou, Y.-l. Liu, S.-h. Pan, H.-z. Zhang, D.-p. Yu, et al., "Raman
edges at the nanowire tips: a cascade cold cathode with two-stage field amplification,"
[31] A. Jha, R. Roy, D. Sen, and K. K. Chattopadhyay, "Curvature aided efficient axial field
wire substrate," Applied Surface Science, vol. 366, pp. 448-454, 2016.
[32] W.-F. Kuan and L.-J. Chen, "The preparation of superhydrophobic surfaces of
[33] Y. Coffinier, G. Piret, M. R. Das, and R. Boukherroub, "Effect of surface roughness and
19 | P a g e
[34] A. Egatz-Gomez, R. Majithia, C. Levert, and K. E. Meissner, "Super-wetting, wafer-sized
silicon nanowire surfaces with hierarchical roughness and low defects," Rsc Advances,
20 | P a g e