parallel arrangements forming a lattice of trigonal symmetry. Each atom has two neighbors in the chain and four
neighbors in adjacent chains situated in a further distance. Covalent bonds dominate intrachain interactions while the
interchain interactions are weaker governed by van der Waals forces. Monoclinic -, -, and -Se are molecular
crystals composed of eight-membered Se8 rings. Each monoclinic unit cell of -, and -Se contain four Se8
molecules, while that of -Se contains eight molecules. Glassy Se is an amorphous semiconductoer with bandgap
energy Eg 2 eV. Its structure is dominated by long polymeric chains and small amounts of Se8 rings as revealed
recently by Raman scattering5.
Se incorporation into zeolite pores has amply demonstrated over the last two decades is well developed 6-10.
Zeolites provide a well defined pore system of molecular dimensions for the encapsulation of many kinds of
substances. Selenium has been encapsulated to several types of zeolites of anionic frameworks such as FAU (X or Y
and several ion-exchanged forms), LTA, AFI, and MOR. Parameters such as the pore size, the Si/Al ratio, the extraframework ions, determine the Se phase that will be formed in the zeolites void. Depending on the host-guest
interactions the formed Se nanostructures can be either sensitive or stable to ambient conditions. So far there has
been no experimental study of Se confinement in purely siliceous zeolites such as the silicalite-1. Silicalite-1 is a
purely siliceous zeolite and as such, its framework does not have extra-framework cations. It belongs to the 10member ring group and its pore system has two types of channels: straight (5.3 x 5.6 ) and sinusoidal (5.1 x 5.5 )
ones which interconnect vertically forming areas with diameter of 8.9 11. Zeolites have two important advantages
that facilitate optical and light scattering studies of encapsulated Se nanostructures; (a) they are wide band gap
insulators and thus exhibit high transmission at visible wavelengths, and (b) their Raman activity is orders of
magnitude lower than that of Se, thus having no influence on the Raman spectrum of the latter.
In the present article we present a detailed investigation of the optical and vibrational properties of
nanostructured Se confined into the silicalite-1 pore network by means of physical vapor deposition (PVD) method.
The temperature at which PVD was performed was systematically varying over a wide range from 150 to 500 oC.
Our results are in qualitative agreement with recent computer simulations 12 that predicted the existence of a pseudowetting transition temperature located between 200 and 600 oC. Below this transition temperature adsorption takes
place inside the pores, whilst the opposite holds if the procedure takes place at temperatures above the critical one.
Experimental procedure
Vacuum
pump
Furnace
380oC
a)
Furnace
b)
c)
1.3 Characterization
The crystals loaded with Se were characterized by means of Raman Spectroscopy, UV/VIS reflectance
spectroscopy and X-ray diffraction. The X-ray diffraction patterns were acquired in a Bruker D8-Advance.
1.4 Raman Spectroscopy
Fourier transform Raman (FT-Raman) spectra were recorded by means of a Bruker (D) FRA-106/S component
attached to an EQUINOX 55 spectrometer. A R510 diode pumped Nd:YAG laser at 1064 nm operating at 20 mW
was used for Raman excitation. An optical filtering reduced the Rayleigh elastic scattering and, in combination with
a CaF2 beamsplitter and a high sensitivity liquid N 2-cooled Ge-detector, allowed the Raman intensities to be
Results
Figure 2 shows two photographs of the silicalite-1 crystals after the encapsulation of Se at 150 oC and 400oC
respectively. At 150o C the loading procedure was very slow and the color of the crystals was light orange, where at
400o C the residence time was 10 times less and the color obtained was dark red.
a) 150 oC, 764 hrs
Reflectance
Spectroscopy (DRS)
In order to obtain absorption
spectra, since our samples are in
powder form, we measured
diffuse
reflection
spectra.
f ( R )
(1 R ) a
2 R
s
Where a is the absorption coefficient and s the scattering coefficient of silicalite-1which is constant in the spectral
range of interest 1, suggesting that (R) identifies with a.
The determination of the band gap depends on the nature of the optical transition. Trigonal selenium exhibits direct
optical transitions where amorphous selenium indirect ones, as derived from the energy dependence of the
absorption coefficient R at the onset of absorption 12. For direct transitions, the plot of [hv(R)]2 vs. hv is linear at
the absorption edge, where hv is the energy of the phonons. Therefore, the intercept of the energy axis provides the
direct band gap. Respectively, the plot of [hv(R)]1/2 vs. hv is linear at the absorption edge, for indirect transitions.
Again, the intercept of the energy axis will provide the indirect bad gap.
Indirect
2,04
1,79
1,49
1,66
1,73
1,72
1,49
2,05
-
Figure 5: XRD spectra of all prepared samples. (The stars denote the positions of the X-ray peaks of silicalite1 and the dotted lines the peaks of t-Se)
Conclusions
Selenium was successfully encapsulated inside the pores of silicalite-1 by means of Physical Vapor Deposition. The
effect of PVD temperature on the structure and band-gap of the encapsulated selenium was also examined. Analysis
using X-ray diffraction and FT-Raman reveal that at all temperatures t-Se is formed. Furthermore, the FT-Raman
spectra revealed that at PVD temperatures of 350 oC and 400oC a fraction of amorphous selenium was also formed.
Finally, DRS reveal that the optoelectronic properties of the encapsulated Se depend on the PVD temperature.
References
1
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