Ordered Carbon Nanotubes and Globular Opals As a Model of Multiscaling Photonic Crystals
Experimental data on carbon nanotube carpet and synthetic opals have been compared by visible, infrared spectroscopy, and electron microscopy. Spectral features of the objects under study in infrared region are registered. Three regions of abnormal behavior of reflectance and absorbance for carbo...
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Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
2008
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irk-123456789-1190812017-06-04T03:04:15Z Ordered Carbon Nanotubes and Globular Opals As a Model of Multiscaling Photonic Crystals Dovbeshko, G. Fesenko, O. Moiseyenko, V. Gorelik, V. Boyko, V. Sobolev, V. Experimental data on carbon nanotube carpet and synthetic opals have been compared by visible, infrared spectroscopy, and electron microscopy. Spectral features of the objects under study in infrared region are registered. Three regions of abnormal behavior of reflectance and absorbance for carbon nanotube carpet and two regions for opals in the 7000-2000 cm⁻¹ are observed in comparison with the separated nanotubes or SiO₂ globules in disordered states and/or condensed state. The spectroscopic features of the photonic crystals caused by their different microstructures at different length scales and basis for development of a proper model for light propagation through the photonic crystals in the IR region are presented for discussion. 2008 Article Ordered Carbon Nanotubes and Globular Opals As a Model of Multiscaling Photonic Crystals / G. Dovbeshko, O. Fesenko, V. Moiseyenko, V. Gorelik, V. Boyko, V. Sobolev // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2008. — Т. 11, № 4. — С. 392-395. — Бібліогр.: 10 назв. — англ. 1560-8034 PACS 42.70.Qs, 68.37.Hk, 78.67.Ch http://dspace.nbuv.gov.ua/handle/123456789/119081 en Semiconductor Physics Quantum Electronics & Optoelectronics Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
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Digital Library of Periodicals of National Academy of Sciences of Ukraine |
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| language |
English |
| description |
Experimental data on carbon nanotube carpet and synthetic opals have been
compared by visible, infrared spectroscopy, and electron microscopy. Spectral features of
the objects under study in infrared region are registered. Three regions of abnormal
behavior of reflectance and absorbance for carbon nanotube carpet and two regions for
opals in the 7000-2000 cm⁻¹ are observed in comparison with the separated nanotubes or
SiO₂ globules in disordered states and/or condensed state. The spectroscopic features of
the photonic crystals caused by their different microstructures at different length scales
and basis for development of a proper model for light propagation through the photonic
crystals in the IR region are presented for discussion. |
| format |
Article |
| author |
Dovbeshko, G. Fesenko, O. Moiseyenko, V. Gorelik, V. Boyko, V. Sobolev, V. |
| spellingShingle |
Dovbeshko, G. Fesenko, O. Moiseyenko, V. Gorelik, V. Boyko, V. Sobolev, V. Ordered Carbon Nanotubes and Globular Opals As a Model of Multiscaling Photonic Crystals Semiconductor Physics Quantum Electronics & Optoelectronics |
| author_facet |
Dovbeshko, G. Fesenko, O. Moiseyenko, V. Gorelik, V. Boyko, V. Sobolev, V. |
| author_sort |
Dovbeshko, G. |
| title |
Ordered Carbon Nanotubes and Globular Opals As a Model of Multiscaling Photonic Crystals |
| title_short |
Ordered Carbon Nanotubes and Globular Opals As a Model of Multiscaling Photonic Crystals |
| title_full |
Ordered Carbon Nanotubes and Globular Opals As a Model of Multiscaling Photonic Crystals |
| title_fullStr |
Ordered Carbon Nanotubes and Globular Opals As a Model of Multiscaling Photonic Crystals |
| title_full_unstemmed |
Ordered Carbon Nanotubes and Globular Opals As a Model of Multiscaling Photonic Crystals |
| title_sort |
ordered carbon nanotubes and globular opals as a model of multiscaling photonic crystals |
| publisher |
Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
| publishDate |
2008 |
| url |
http://dspace.nbuv.gov.ua/handle/123456789/119081 |
| citation_txt |
Ordered Carbon Nanotubes and Globular Opals As a Model of Multiscaling Photonic Crystals / G. Dovbeshko, O. Fesenko, V. Moiseyenko, V. Gorelik, V. Boyko, V. Sobolev // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2008. — Т. 11, № 4. — С. 392-395. — Бібліогр.: 10 назв. — англ. |
| series |
Semiconductor Physics Quantum Electronics & Optoelectronics |
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2025-07-08T15:11:42Z |
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| fulltext |
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2008. V. 11, N 4. P. 392-395.
© 2008, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
392
PACS 42.70.Qs, 68.37.Hk, 78.67.Ch
Ordered carbon nanotubes and globular opals
as a model of multiscaling photonic crystals
G. Dovbeshko1, O. Fesenko1, V. Moiseyenko2, V. Gorelik3, V. Boyko1 and V. Sobolev4
1Institute of Physics, NAS of Ukraine, 46, prospect Nauky, 03028 Kyiv, Ukraine
2Dnipropetrovsk National University, 72, prospect Gagarina, 49050 Dnipropetrovsk, Ukraine
3P.N. Lebedev Physics Institute Russian Academy of Sciences, 53, Leninsky prospect, Moscow 117924, Russia
4Technical Centre of NASU, 13, Pokrovskaya str., 04070 Kyiv, Ukraine
Abstract. Experimental data on carbon nanotube carpet and synthetic opals have been
compared by visible, infrared spectroscopy, and electron microscopy. Spectral features of
the objects under study in infrared region are registered. Three regions of abnormal
behavior of reflectance and absorbance for carbon nanotube carpet and two regions for
opals in the 7000-2000 cm-1 are observed in comparison with the separated nanotubes or
SiO2 globules in disordered states and/or condensed state. The spectroscopic features of
the photonic crystals caused by their different microstructures at different length scales
and basis for development of a proper model for light propagation through the photonic
crystals in the IR region are presented for discussion.
Keywords: photonic crystal, opal, carpet of carbon nanotubes, IR spectra, phonon mode,
Bragg scattering.
Manuscript received 26.09.08; accepted for publication 00.00.08; published online 00.00.08.
1. Introduction
Photonic crystals as a new class of materials take place
between nano- and microstructural highly ordered
composites. Electromagnetic wave propagation through
a structure with sizes of elements close to the
wavelength leads to Bragg diffraction, multiple
scattering, etc. As a result of this process, a forbidden
photonic band arises [1-5]. Photonic crystals with a
tunable forbidden band are of interest for researchers and
technical applications. Our paper is directed to optical
study of photonic crystals – opals and carbon nanotubes
in IR region. Optical characteristics of opal were not
studied in this region due to the fact that opal is a crystal
that is traditionally applied in the visible region [5],
however the SiO4-structural element of SiO2 single
crystal has transparency windows in the IR region [6].
Carbon nanotube is a structure that absorbs light in a
wide wavelength range from UV, through VIS and up to
FIR region. The property of ordered nanotubes
ensembles as a possible model of photonic crystals are
not studied, too. Particularly, assignment of a nanotube
carpet to photonic crystals should be proved. Our goal
was to register the optical characteristics of opals and
carbon nanotubes in IR region that are related with
different size scales of microstructures and connected
with the nature of crystalline material (phonon modes)
and do a step for its modeling.
2. Methods and materials
The samples of carbon nanotubes (CNT) were obtained
by evaporating either a solid carbon precursor (camphor)
or a liquid one (cyclohexanol) on silicon substrates. The
process of synthesis involves the coevaporation of the
carbon precursor and ferrocene, used as the catalyst
source, in nitrogen atmosphere [7]. The nanotubes were
well packed, vertically aligned, multi walled and several
millimeters in length.
Synthetic opals were produced in Zelenograd
(Russia) and Dnepropetrovsk (Ukraine). Nanodisperse
silica globules were synthesized by the method of Stober
et al. through the hydrolysis of tetraethoxysilane
Si(OC2H5)4 in water-ethanol solution in the presence of
ammonium hydroxide as catalyst. The molar ratio of
components in the reaction mixture was as follows:
NH4OH:H2O:C2H5OH:Si(OC2H5)4=(0.1-1):(2-20):(11-
14):0.14.
Structure of the samples and their optical properties
has been characterized by SEM analysis and FTIR
reflectance and absorbance spectroscopy, respectively.
IR spectra have been registered with Bruker IFS-66
FTIR spectrometer in the 7500-400 cm-1 region. SEM
images of opals were obtained with EPMA SEI JXA-
8200 microscope and carbon nanotubes images – with
JSM-35 microscope.
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2008. V. 11, N 4. P. 392-395.
© 2008, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
393
3. Results and discussion
According to M. Barabanenkov [1] and V. Kosobukin
[2], a definition of photonic crystals or existence of
forbidden photonic band (FPB) could be based on the
following features: periodicity in three dimensions;
small absorbance (multiple scattering); dielectric
contrast n1/n2 > 2/3; a volume ratio of structural units of
a photonic crystal to pore filling environment should be
small; structure is good when optical path in both
materials is the same; deviation in sizes is much less
than the average particle size: ∆R << Ravg; displacement
of the structural elements is much less than a distance
between the elements of the structure: ∆u << a.
Taking into account the abovementioned criteria
and dielectric constants for silica and graphite materials
[8], we could suppose from SEM image analysis that
carpet of nanotubes (Fig. 1) and synthetic opal (Fig. 2)
could be assigned to photonic crystals. For photonic
crystals, a simple equation for Bragg diffraction could be
written as: λmax = 2dhkl neff sinθ, where neff =
[(ns)2f + (np)2(1 – f)]1/2, d = (2/3)1/2a, a – characteristic
size (diameter) of the structural element of photonic
crystal, d – distance between elements, f = 0.74 [3]. CNT
carpet has a microstructure of a different scale – from
micrometers to millimeters. For example, a characteristic
size of structure granularity is 0.05-0.1 µm (Fig. 1a, c),
2-10 µm (Fig. 1a, c), and 1000-2000 µm (Fig. 1b).
Similar situation is observed with opal having the fine
globular structure with 0.2-0.5 µm size (Fig. 2a), above
the globular structure (2-5 µm) (Fig. 2b, c) and superfine
structure consisting of small balls with 0.05 µm size [9].
So, we suppose that photon stop bands could exist in
visible and IR regions up to far-IR in the objects under
study, if the main conditions for FPZ will be valid. The
spectra presented in Figs 3 to 7 are an evidence of this
asumption. Near-normal incidence IR reflectance spectra
of the CNT carpet (Fig. 4a, b) and opal photonic crystal
(Fig. 5) depend on the sample orientations.
Fig. 3. Bragg reflectance of synthetic opal for two
orthogonal orientations of the crystal in (111) plane at
different angles of light incidence: a – big “axis” of the
sample is parallel to the long axis, b – small “axis” of the
sample is perpendicular to the short one.
a
scale 10 µm
b
scale 100 µm
c
scale 10 µm
Fig. 1. Microstructure (SEM images) of carpet of carbon nanotubes consisting of separated column or blocks: a – top view, b
and c – side view.
a b c
Fig. 2. Microstructure (SEM images in SEI mode) of synthetic opal: a – ordered globules (view from the top); b – globules
organized in terraces of mosaic structure –“strip” type; c – disordering in a microstructure of opal (view from the top).
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2008. V. 11, N 4. P. 392-395.
© 2008, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
394
Fig. 4. Near-normal incidence IR reflectance spectra of the
CNT carpet for different sample orientations: from the bottom
layer of ordered carbon nanotubes (a), from side layers (b).
Spectra of disordered powder of carbon nanotubes are
presented for comparison.
Fig. 5. Near-normal incidence IR reflectance spectra of the
opal photonic crystal for different orientations of the sample: 1
– side layer (111), 2 – bottom layer.
It is known [10] that two types of bands in photonic
crystals could exist: band gaps induced by Bragg
scattering and other band gaps connected with negative
permittivity. The angle dependence of Bragg scattering
(shown in Fig. 3) is typically observed for opal photonic
crystals in the visible range. However, some additional
peaks appear in 6000-1000 cm-1 region for opal, while
they absent in solid silica (Fig. 5). We found a narrowing
of the phonon band of opal in comparison with any solid
crystal forms of silica. The halfwidth of the stretching
vibration band (Fig. 6) for opal is 44 cm-1 and less than
those for fused quartz, namely, 88 cm-1 and α-quartz,
102 cm-1.
We wanted to use opal for enhanced IR absorption
of biological molecules. So, we drop poly A water
solution on opal surface. Saturation of opal pores by
poly-A water solution causes to appearance of new
bands in reflectance at 6000 and 4500 cm-1 (Fig. 7,
curve 3).
Fig. 6. Normalized IR reflectance spectra of single crystal of
α-quartz (1), fused quartz (2) and opal crystal (3) in the region
of stretching vibration (band of negative dielectric function).
Fig. 7. IR reflectance spectra of initial opal after heating (1),
opal with drop of the aqueous solution of poly-A just after drop
deposition on the crystal surface (2) and dried film of poly-A
on the opal surface (3).
IR reflectance spectra of opal with drop of the
aqueous solution of polyadenylic acid (poly-A) just after
drop deposition on the opal surface (Fig. 7, curve 2) and
dried film of poly-A on the opal surface (Fig. 7, curve 3)
demonstrate only bands that can be assigned to the
stretching vibration of opal (1300-900 cm-1), deformation
vibration (500-400 cm-1). The bands of poly-A molecular
vibrations are absent in this spectrum. That is why opal
cannot be used for enhanced IR absorption of biological
molecules. We suppose that elongated structures like
cylinder, rod and strip create a forbidden band near
6000 cm-1, like balls – in the 2000-5000 cm-1. However, it
needs a theoretical proof. Observed peculiarities in the IR
spectra depend on a change of scale for the structure, very
sensitive to disordering and do not depend on the
molecular structure (phonon modes) of the material. Note
that the Bragg gap is sensitive to disordering, whereas
negative band induced by dielectric permittivity are
insensitive to disordering.
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2008. V. 11, N 4. P. 392-395.
© 2008, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
395
In conclusion, a number of spectral peculiarities in
the spectra of synthetic opals and ordered carbon
nanotubes in the IR region were observed. These
features indicate the narrowing of known phonon bands
(negative ones) and appearance of new photon stop
bands. A new theoretical approach should be developed
for description of these processes. We suppose that the
experimental data and ideas presented here could help to
develop a theoretical model as well as open a new
application of photonic crystals for optical filters, lenses,
etc.
Acknowledgements
We thank Ukrainian Program – Nanostructured Systems,
Nanomaterials, Nanotechnology, (“Bionanosystems”
N0107U008449, 2007-2009) for financial support, Prof.
Alberto Tagliaferro and his group from Torino
Polithechnical Institute (Italy) for carpet nanotube
production as well as for fruitful discussions and Dr.Sci.
Viktor Stepkin from Institute of Physics, NAS of
Ukraine (Kyiv) for SEM images of CNT carpet.
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