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Second International Symposium, Advanced micro- and mesoporous materials 2007

September 6-9, 2007, Varna, Bulgaria

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

1.1 Synthesis of silicalite-1


Silicalite-1 crystals were prepared using a procedure found in the literature 13. The synthesis sol was prepared by
adding 26 ml of Tetraethoxysilane (TEOS) to a solution of 25ml H 2O, and 45 ml Tetrapropylammonium Hydroxide

Second International Symposium, Advanced micro- and mesoporous materials 2007


September 6-9, 2007, Varna, Bulgaria
(TPAOH, 1M) (25 SiO2 / 9 TPAOH / 480 H2O / 100 t). It was then heated at 85 oC for 24 hrs. The crystals were
purified by repeated centrifugation and were calcined at 420oC for 6hrs

1.2 Physical Vapor Deposition (PVD)


Se was encapsulated in the crystals using Physical Vapor Deposition. In order to perform PVD the appropriate cell
was prepared. A Pyrex tube was sealed at one end and open at the other. In the middle a stenosis was made in order
to avoid the mixing of selenium beads with that of the silicalite-1 crystals. A pre-calculated amount of silicalite-1
crystals were placed at the bottom of the PVD cell. The appropriate mass of selenium beads was placed above the
stenosis. Prior to PVD the samples were degassed overnight at 380 oC (Figure 1.a). Special care was taken so that the
temperature at the Se beads was kept close to room temperature and that only the zeolite powder was heated at
380oC. The cell was then vacuum-sealed and horizontally placed in the furnace that was preheated at the desired
temperature (Figure 1.b & 1.c). The PVD was terminated when the Se/MFI crystals obtained a homogeneous reddish
color. The PVD duration was significantly affected by the temperature and it was ~765 hrs at 150 oC and ~50 hrs at
500oC. After the end of the PVD the sample was slowly cooled down at room temperature. It also has to be
mentioned that at all times the temperature at both sides of the cell was the same in order to avoid deposition by
sublimation.

Vacuum
pump

Furnace
380oC

a)

Furnace

b)

c)

Figure 1: Representation of experiments steps

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

Second International Symposium, Advanced micro- and mesoporous materials 2007


September 6-9, 2007, Varna, Bulgaria
recorded over a broad spectral region in the anti-Stokes and Stokes region with a resolution of about 1 cm -1. Spectra
were recorded from Se/zeolite powder sealed under vacuum in pyrex ampoules.

1.5 UV/VIS Diffuse Reflectance spectroscopy.


A cary 13 spectrophotometer equiped with integration sphere was used to measure the diffuse reflectance of the
samples loaded in a cuvette. The spectra were collected at ambient conditions and as reference sample we used
crystals of silicalite-1diluted to -Al 2O3. For the Kubelka-Munk function to apply, the reflection ((R)) must be in
the range of 0,2 - 0,6 11. Therefore the samples had to be diluted accordingly, i.e. 0,0081g of Se/MFI powder diluted
with 0,9455g of -Al2O3. The same ratio was used in the reference sample.

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

b) 400 oC, 75 hrs

Figure 2: Differences between loaded crystals at two PVD temperatures

FT- Raman Spectroscopy


An important advantage of the present Raman study is the use of a near infrared laser (1064 nm or 1.165 eV) which
implies purely off-resonant conditions of Raman spectra excitation as opposed to all previous studies where light
energy comparable to bandgap energy was utilized. Raman spectra obtained from the Se/zeolite nanocomposites
sealed in the ampoule are presented in Fig. 3. For reasons explained above the Raman response of the zeolite matrix
is practically absent from the spectrum. This figure reveals the Raman spectrum of confined Se changes drastically
when the PVD temperature increases above 300 oC. At low temperatures of the PVD process the high frequency
Raman spectrum is dominated by a doublet located at ~234 and 237 cm -1. These two peaks are the characteristic
stretching intrachain modes of t-Se and have been assigned to the E and A1 symmetry modes, respectively14. Since
no other vibrational modes characteristic of other forms of Se appear at these low temperatures of confinement it can
be concluded that confined that isolated Se chains form within the zeolite pore network. It is further important to

Second International Symposium, Advanced micro- and mesoporous materials 2007


September 6-9, 2007, Varna, Bulgaria
notice that the difference between the E and A1 modes is not constant but varies with the PVD temperature. This
could probably originate either from the fact that the chains that grow in the pore network have slightly different
distortions or from the different degree of interaction between Se and pore wall.
An abrupt change of the Raman spectrum is observed when the PVD temperature increases above 300 oC. In
particular, a very broad, asymmetric peak develops at the high energy side of the t-Se spectrum. This new band is
peak at ~250 cm-1 but its spectral envelope contains at least more than two peaks. The band at 250 cm -1 is
characteristic of glassy Se while at even high energy (~260 cm-1) the vibrational modes are signatures of Se8 ringlike
species 5.

Figure 3: FT-Raman spectra


of Se/MFI at all PVD
temperatures
Diffuse

Reflectance

Spectroscopy (DRS)
In order to obtain absorption
spectra, since our samples are in
powder form, we measured
diffuse

reflection

spectra.

Diffuse reflection (R) was then


converted into the KubelkaMunk function (R) :

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.

Second International Symposium, Advanced micro- and mesoporous materials 2007


September 6-9, 2007, Varna, Bulgaria
In figure 4 we compare the plots of [hv (R)]2 vs. hv for all PVD temperatures assuming direct optical transitions
as that of trigonal selenium. For all samples, both transitions were plotted and the obtained band gap results are
tabulated in Table 1 together with the band gaps of bulk forms of selenium (a-Se and t-Se). Only at one PVD
temperature (150oC) the band gap of confined selenium was higher than that of the bulk.

Table 1 Band Gaps of Se/MFI and of a-Se and t-Se3


PVD Temperature
150
200
250
300
350
400
500
a-Se
t-Se

Band Gap (eV)


Direct
2,11
1,92
1,59
1,72
1,79
1,80
1,58
1,95

Figure 4 Plot of [hv(R)]2 vs hv assuming direct band gap

X-Ray diffraction spectroscopy

Indirect
2,04
1,79
1,49
1,66
1,73
1,72
1,49
2,05
-

Second International Symposium, Advanced micro- and mesoporous materials 2007


September 6-9, 2007, Varna, Bulgaria
The X-ray diffraction patterns of the crystals at different PVD temperatures are shown in Figure 5. In all cases the
diffraction peaks of silicalite-1 (stars) and of t-Se (dotted lines) can be observed, supporting the analysis of the
Raman spectra.

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.

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