Sains Malaysiana 48(8)(2019): 1745–1752
http://dx.doi.org/10.17576/jsm-2019-4808-21
Novel Surface-Enhanced
Raman Scattering Substrate based on Functionalized Silicon Nanowires
(Raman Permukaan-Dipertingkatkan
Sebaran Substrat Baru berasaskan Silikon Berfungsi Wayar Nano)
IRAM MAHMOOD1*, ISHAQ AHMAD2,3 & ISHFAQ AHMAD4
1Department
of Industrial Engineering, College of Engineering, King Khalid University Abha
61413, Kingdom of Saudi Arabia
2National
Center for Physics, Islamabad, 44000, Pakistan
3NPU-NCP
Joint
International Research Center for Advanced Nanomaterials and Defects
Engineering, Northwestern Polytechnical University, Xi'an 710072,
China
4Department
of Mathematics and Statistics, Faculty of Basic and Applied Sciences,
International Islamic University, Islamabad, Pakistan
Diserahkan: 11
Februari 2019/Diterima: 21 Mei 2019
ABSTRACT
This study reports synthesis
of a new Surface-Enhanced Raman Scattering (SERS)
substrate using Silicon nanowires (SiNW's) arrays, produced through
chemical etching, and functionalized by tailoring their surface
chemistry with nitrogen containing groups. From SEM characterization, phenomenon of micro
channel formation, porosity and amorphous nature for the as prepared
SiNWs was observed. Photoluminescence (PL) spectrum showed that these
nanowires have broad emission band in the range of 500-900 nm.
Also, change in the surface chemistry of Si nanowires after nitrogen
treatment was observed by elemental analysis, EDX and X-ray photoelectron spectroscopy.
The data showed that raising the modification temperature also
increased the nitrogen content. At high temperature, pyridine
and aromatic amines were the dominant functional groups while
a small amount of quaternary nitrogen and protonated amide were
also present. Methylene blue (MB)
was used as a probe molecule to investigate SERS activities
of functionalized SiNWs. The enhancement factor was estimated
to be 107-109.
Interaction of nitrogen containing groups on the surface of SiNWs
with MB molecules resulted in high adsorption of MB on the substrate and higher
signal detection by SERS.
Keywords: Methylene
blue; photoluminescence; Raman scattering; surface enhanced Raman scattering;
silicon nanowires
ABSTRAK
Kajian ini melaporkan
sintesis substrak Raman Permukaan-Dipertingkatkan Sebaran (SERS)
menggunakan susunan nanowayar silikon melalui proses punaran secara
kimia, serta penukaran sifat kimia permukaan dengan kumpulan berfungsi
bernitrogen. Melalui pencirian SEM, pembentukan saluran mikro, liang
dan ciri-ciri amorfous telah diperhatikan. Spektrum fotoluminesens
menunjukkan bahawa nanowayar yang terhasil mempunyai jalur pancaran
lebar dalam julat 500-900 nm. Di samping itu, perubahan kimia
permukaan nanowayar selepas rawatan nitrogen telah dikaji dengan
analisis unsur, EDX dan
spektroskopi fotoelektron sinar-X. Data yang diperoleh menunjukkan
bahawa ubahsuaian melalui suhu juga meningkatkan kandungan nitrogen.
Pada suhu tinggi, piridina dan amina aromatik adalah kumpulan
berfungsi utama dengan terdapat kandungan kecil nitrogen kuaternari
dan amida juga terbentuk. Metilena biru (MB)
telah digunakan sebagai molekul model untuk mengkaji aktiviti
SERS bagi
substrak SiNWs yang terhasil. Faktor peningkatan sebanyak 107-109
telah diperoleh. Interaksi antara kumpulan berfungsi
nitrogen pada permukaan SiNWs dan molekul MB menyebabkan penjerapan MB yang
tinggi, lalu mencapai pengesanan isyarat SERS yang tinggi.
Kata kunci:
Fotoluminesens; metilena biru; serakan Raman; serakan Raman permukaan dipertingkatkan;
silikon nanowayar
RUJUKAN
Baia,
L., Baia, M. & Popp, A.J. 2006. Gold films deposited over regular arrays of
polystyrene nanospheres as highly effective SERS substrates from visible to
NIR. J. Phys. Chem. B. 110(47): 23982-23986.
Chun,
H.E. & Xijun, H.U. 2011. Anionic dye adsorption on chemically modified
ordered mesoporous carbons. Ind. Eng. Chem. Res. 50(24): 14070-14083.
Cotton,
T.M., Kim, J.H. & Chumanov, G.D. 1991. Application of surface-enhanced
Raman spectroscopy to biological-systems. J. Raman Spectrosc. 22(12):
729-742.
Green,
M. & Liu, F.M. 2003. SERS substrates fabricated by island lithography: The
silver/pyridine system. J. Phys. Chem. B 107(47): 13015-13021.
Hulchineon,
K., Heater, R., Albery, J. & Hillman, A.R. 1984. Raman Spectroscopic
studies of a thionine modified electrode. J. Chem. Soc. Faraday Trans. 80:
2053-2071.
Kneipp,
K., Wang, Y., Kneipp, H., Perelman, L.T., Itzkan, I., Dasari, R.R. & Feld,
M.S. 1997. Single molecule detection using surface-enhanced raman scattering. Phys.
Rev. Lett. 78(9): 1667-1670.
Laurent,
G., Fe´lidj, N., Aubard, J., Le´vi, G., Krenn, J.R., Hohenau, A., Schider, G.,
Leitner, A. & Aussenegg, F.R. 2005. Evidence of multipolar excitations in
surface enhanced Raman scattering. Phys. Rev. B. 71(4): 045430.
Li, B.,
Yu, D. & Zhang, S. 1999. Raman Spectral study of silicon nanowires. Phys.
Rev. B 59(3): 1645-1648.
Naujok,
R.R., Duevel, R.V. & Corn, R.M. 1993. Fluorescence and Fourier transform
surface-enhanced Raman scattering measurements of methylene blue adsorbed onto
a sulfur-modified gold electrode. Langmuir 9(7): 1771-1774.
Nie, S.
& Emory, S.R. 1997. Probing single molecules and single nanoparticles by
surface-enhanced Raman scattering. Science 275(5303): 1102-1106.
Pavan,
G.V., Kumar, S., Shruthi, B., Vibha, B.A., Ashok, R., Kundu, T.K. &
Narayana, C. 2007. Hot spots in Ag core- Au shell nanoparticles potent for
surface-enhanced Raman scattering studies of biomolecules. J. Phys. Chem. C. 111(11): 4388-4392.
Qianwang,
C., Zhu, J., Lia, X.G., Fanab, C.G. & Zhang, Y.H. 1996. Photoluminescence
from porous silicon obtained by hydrothermal etching. Physics
Letters A 220(4-5): 293-296.
Ruan,
C., Luo, W., Wang, W. & Gu, B. 2007. Single-molecule detection of thionine
on aggregated gold nanoparticles by surface enhanced Raman scattering. J.
Raman Spectrosc. 38(5): 568-573.
Tian,
J.H., Liu, B., Li, X., Yang, Z.L., Ren, B., Wu, S.T. & Tian, Z.Q. 2006.
Study of molecular junctions with a combined surface-enhanced Raman and
mechanically controllable break junction method. J. Am. Chem. Soc. 128(46):
14748- 14749.
Torchynska,
T.V., Cano, A.D., Rodriguez, M.M. & Khomenkova, L.Y. 2003. Hot carriers and
excitation of Si/SiOx interface defect photoluminescence in Si nanocrystallites. Physica B 340: 1113-1118.
Xiao,
G.N. & Man, S.Q. 2007. Surface-enhanced Raman scattering of methylene blue
adsorbed on cap-shaped silver nanoparticles. Chemical Physics Letters 447(4):
305-309.
Zhang,
M.L., Fan, X., Zhou, H.W., Shao, M.W., Zapien, J.A., Wong, N.B. & Lee, S.T.
2010. A high-efficiency surface-enhanced Raman scattering substrate based on
silicon nanowires array decorated with silver nanoparticles. J. Phys. Chem.
C 114(5): 1969-1975.
Zhang,
M.L., Peng, K.Q., Fan, X., Jie, J.S., Zhang, R.Q., Lee, S.T. & Wong, N.B.
2008. Preparation of large-area uniform silicon nanowires arrays through
metal-assisted chemical etching. Phys. Chem. C 112(12): 4444-4450.
*Pengarang untuk surat-menyurat;
email: irahmad@kku.edu.sa