Materials Chemistry and Physics 133 (2012) 850856

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Materials Chemistry and Physics
j our nal homepage: www. el sevi er . com/ l ocat e/ mat chemphys
Connement of zinc oxide nanoparticles in ordered mesoporous silica MCM-41
P.B. Lihitkar
a
, Samuel Violet
b
, Mandar Shirolkar
a,d
, Jai Singh
c
, O.N. Srivastava
c
, R.H. Naik
b
, S.K. Kulkarni
d,
a
DST Unit on Nanoscience, Department of Physics, University of Pune, Pune, India
b
National Chemical Laboratory, Pashan Road, Pune, India
c
Department of Physics, Banaras Hindu University (BHU), Varanasi, India
d
Indian Institute for Science Education and Research (IISER), Pune, India
a r t i c l e i n f o
Article history:
Received 5 March 2011
Received in revised form
25 September 2011
Accepted 29 January 2012
Keywords:
Mesoporous
Photoluminescence spectroscopy
Surface properties
Defect
Energy spectroscopy for chemical analysis
(ESCA)
a b s t r a c t
Mesoporous silica (MS) and zinc loaded MS composites have been synthesized and characterized using
high resolution transmission electron microscopy, X-ray diffraction, UVvisible spectroscopy, photolu-
minescence spectroscopy, N
2
adsorptiondesorption isotherms, X-ray photoelectron spectroscopy and
Fourier transform infrared spectroscopy. Thermal treatment of the zinc loaded MS composite lead to the
formation of ZnOMS composite. The well ordered uniform pore structure of MS (pore size 3.4nm) is
found to remain stable even after 30% Zn loading albeit decrease in the pore size 1.2 nm indicates the
formation of ZnO inside the pores.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Zinc oxide is a direct band gap semiconductor having band gap
energy of 3.37eV. It has a large exciton binding energy (60meV)
which allows the excitonic emission even at room temperature
[13]. Due to its large band gap energy, it is useful in the visible
light emission applications as well as in ultraviolet/blue emis-
sion devices like in lasers, diodes, solar cells and in acoustic
devices [46]. Different morphologies of ZnO nanostructures such
as nanowires, nanobelts, nanorods, nanospheres have been pre-
pared [7]. However, synthesis of ZnO nanoparticles in the desired
dimension has limitations due to difculties in controlling the
nanoparticle aggregation. Ordered porous materials offer a very
good option to not only retain the nanoparticle size but also to
order the particles which can be useful in many applications.
Mesoporous silica (MS) has uniform channels with pore diam-
eter from 2 to 50nm which can be used to control the size
of nanoparticles during their growth. Silica mesoporous material
MCM-41, a member of M41S family exhibits hexagonal arrange-
ment of uniform pores [8]. Semiconductor nanoparticles such as
PbS, CdS, ZnS, TiO
2
and ZnO [920] have been incorporated inside
the mesoporous solidMCM-41by using various synthesis methods.

Corresponding author. Tel.: +91 20 25888032.

E-mail address: s.kulkarni@iiserpune.ac.in (S.K. Kulkarni).
ZnOnanocrystals are loaded inside the MCM-41 by functionalizing
the surface of MCM-41 using ethylene diamine [14,15]. It was pro-
posed that the negative charge on the functional group prefers to
bind with the positively charged Zn ions through chelation. How-
ever one cannot avoid the possibility of Zn ions getting bound with
external surface of the silica because functionalization will be all
over the surface. Vaishanvi et al. [16] have in situ prepared ZnO in
the pores of host mesoporous silica whereas Xiong et al. [17] have
grafted ZnO nanoparticles within MCM-41 using impregnation
method. In addition to this, Dapurkar et al. [18] have synthesized
ZnO nanoparticles using impregnation method and Zeng et al. [19]
have in situ generated ZnO clusters inside MCM-41 by an aqueous
chemical growth method. Burova et al. [20] have suggested ZnO
nanoparticles synthesis inthemesoporous silica matrixbyincorpo-
rating hydrophobic Zn precursor such as Zn acetylacetonate in the
hydrophilic mesoporous silica which shows considerable ultravio-
let emission (I
UV
/I
Vis
=65) as compared to bulk ZnO. Optical study
of conned ZnO nanoparticles inside the three dimensional zeo-
lites is also investigated by Bouvy et al. [21] and Chen et al. [22].
The reverse micelle strategy as well as colloidal method has been
utilized for the preparation of ZnO in large pore mesoporous silica
CMI-1 [23]. Mesoporous ZnOSiO
2
nanocomposites have also been
investigated by Fernandez et al. using one pot, surfactant assisted
method [24,25]. It is observed that some of the Zn atoms are also
present in the silica framework which creates strain on the silica
wall leading to the distortion in pores. Albero et al. [26] proposed
the synthesis of zinc modied MCM-41 spheres for different Zn/Si
0254-0584/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2012.01.106
P.B. Lihitkar et al. / Materials Chemistry and Physics 133 (2012) 850856 851
Fig. 1. (A) Small angleXRDof calcinedmesoporous silica(MS) andZnOMSsamples havingdifferent weight percent (130%) of Zn. (B) Wide-angleXRDpatterns of mesoporous
silica and ZnOMS samples. The bars on X-axis showplanes due to bulk ZnO (JCPDS le no 80-0075).
ratios. For lower Zn/Si ratio (0.02), Zn is found to be in the frame-
work where as for higher ratio (0.04) the distortion in the long
range order is observed. Martins et al. [27] have preparedthe meso-
porous ZnO:SiO
2
lmby the solgel and dip coating method. They
have studied the effect of the withdrawal speed of dipped lm on
the microstructure and optical properties of mesoporous ZnO:SiO
2
lms
Encapsulation of ZnO inside zeolite pores is limited due to
its small pore size (<2nm). However, the methods which have
been utilized for the preparation of ZnO nanoparticles within the
mesoporous cavity of MCM-41 are not efcient as the ZnO is an
amphoteric oxide material due to which template structure col-
lapses in acidic and basic mediumleading to the template removal.
In most of the cases, it is observed that ZnO nanoparticles are
Fig. 2. (A) N
2
adsorptiondesorption isothermand (B) pore size distribution plot of MS and 30% Zn loaded ZnOMS samples.
852 P.B. Lihitkar et al. / Materials Chemistry and Physics 133 (2012) 850856
Table 1
Surface area and pore size obtained fromN
2
-adsorption/desorption isotherm.
Sample BET surface area S
A
(m
2
g
1
) BJH pore volume (cc g
1
) BJH average pore size (nm)
MS 1100 0.70 3.368
30% ZnMS 841.5 0.60 2.202
anchored on the external surface. Attempts have been made by
Jiang et al. [13] to overcome these limitations using solid state
reaction to incorporate ZnO within the cavity of mesoporous silica
SBA-15. This method was found to be more effective as compared
to those reported earlier.
In the present work, we report the preparation of ZnO inside
the MCM-41 mesoporous silica using solvent free method. Pris-
tine mesoporous silica and salt of zinc nitrate are ground together
followed by controlled heating in air. This leads to the incorpo-
rated ZnO nanoparticles inside the pores without damaging the
MCM-41 structure. We believe that, so far there is no report of
such type of work. ZnO incorporated mesoporous silica (MS) is
thoroughly analyzed with different characterization techniques in
order to understand the morphology and properties of ZnOMS
nanocomposites.
2. Materials and methods
Zinc nitratehexa-hydrate[Zn(NO
3
)
2
6H
2
O] was purchasedfrom
Thomas Baker company and cetyl trimethyl ammonium bromide
(CTAB), C
16
H
33
N(CH
3
)
3
Br were purchased fromMolychem, India.
Tetra methyl ammonium hydroxide ([(CH
3
)
4
NOH] TMAOH) and
Fig. 3. HR-TEMimage of the calcined mesoporous silica MCM-41 (A) and ZnOMS
sample having 30% Zn loading (B). Inset in (A) and (B) shows the electron diffraction
rings. Another inset in (B) shows HR-TEM image of ZnOMS sample taken with
beam direction perpendicular to the pores. Electron diffraction (inset B) indicates
the plane due to hexagonal ZnO crystals.
fumed silica were purchased fromKemphasol and Sigma company
respectively.
Mesoporous silica was synthesized by the method reported
in our earlier work [12]. The molar composition of the
initial mixture for the mesoporous silica synthesis was
SiO
2
:0.25CTAB:0.2TMAOH:40H
2
O. In a typical synthesis, 4.55g of
CTAB was dissolved in 33.3ml of milli-Q water by stirring it for
45minutes at roomtemperature (RT). 3.5ml of TMAOHwas added
after complete dissolution of the surfactant and allowed to stir for
1h. After adding 3g of fumed silica, the resultant gel was kept on
stirring at high speed for 3h. The pH of the resulting gel was 12.3
which after aging the gel for 24h at RT slightly decreased to 12.2.
The foam like uniform gel was loaded in an autoclave and heated
hydrothermally at 135

C for 48h. The resultant solid product was

ltered, washed with plenty of water and dried at 60

C for 23h.
For the ZnO loading inside the mesoporous silica, different
weight percent (1%, 2%, 3%, 4%, 5%, 10%, 20%, 30%) of Zn(NO
3
)
2
6H
2
O
was mixed with pristine mesoporous silica by grinding it in the
mortar. The resultant mixture was heated at 540

C for 5h in the
tube furnace by controlled heating at a rate of 23

Cmin
1
in an
open atmosphere. The structure and crystallinity of the ZnOMS
samples were characterized using small and wide angle X-ray
diffraction(XRD) whichwereperformedonanX-raydiffractometer
(Rigaku miniex) using CuK radiation source (=0.154nm).
Fig. 4. Diffuse reectance UVVis spectra of calcined MS and ZnOMS samples for
different weight percent of Zn loading 130% Zn loading.
P.B. Lihitkar et al. / Materials Chemistry and Physics 133 (2012) 850856 853
The N
2
adsorptiondesorption isotherms were obtained using
Quantachrome Autosorb automated gas sorption system under
continues adsorption condition. BrunauerEmmettTeller (BET),
BarretJoynerHalenda (BJH) methods were used to determine
total specic surface area (S
BET
) and pore size distribution respec-
tively of the MS and resultant ZnOMS samples. For this, P/P
0
=0.99
was used. Here, P is pressure at which gas is adsorbed and P
0
is
saturation vapour pressure of adsorbate.
UVvisible absorbance and photoluminescence of ZnOMS
powder samples were performed by using Perkin Elmer instru-
ments Lambda 950 and LS-55 respectively. Fourier TransformInfra
Red (FT-IR) analysis of the samples was made using Thermo Scien-
tic Nicolet 6700 instrument. KBr was used as standard reference
and was mixed with the samples in order to take the IR spectra.
X-ray photoelectron spectroscopy (XPS) analysis of the dry pow-
der samples was made using Omicron ESCA, UK instrument using
MgK (energy=1253.6eV) source of X-rays and concentric hemi-
spherical analyzer with 50eV pass energy.
3. Results and discussions
ZnO nanoparticles are conned in the mesoporous silica (MS)
by the decomposition of pristine MS and zinc nitrate salt using
controlled thermal treatment. Fig. 1A illustrates the small angle
XRD patterns of the calcined MS and different weight percent of
Zn loaded ZnOMS samples. They exhibit a strong diffraction peak
due to (100) plane. Small intensity peaks due to (110) and (200)
planes also appeared in all the samples. This indicates that the
mesoporous structure in the ZnOMS sample remains intact. The
XRD pattern of calcined MS having 2 =1.75

and d=5.05nmvalue
conrmthe presence of mesoporous structure of MCM-41 [8].
Introduction of ZnO inside the MS for all the samples leads to a
small shift of diffractionpeaks to a slightly lower angle withrespect
to the peak due to calcined MS as shown in Fig. 1A. The slight shift
in the diffraction peaks may be due to an increase in the interplanar
distances of the hexagonal structure of the MS sample. In ZnOMS
samples, small peaks due to (100), (101) and (002) planes of
hexagonal ZnO were observed in the XRD patterns as shown in
Fig. 1B. Althoughthe XRDpeaks due toZnOare of very lowintensity
they are consistent with some earlier reports on similar systems.
Jiang et al. [13] did not observe any diffraction peaks due to ZnO
even for 30% Zn in SBA-15. Similarly Wang et al. [28] also reported
low intensity XRD peaks due to CuO in case of CuO/SBA-15. We
shall show using TEMand N
2
adsorptiondesorption analysis that
ZnO is indeed present inside the pores of the MS.
The mesoporous structure of the MS and ZnOMS after calcina-
tions at 550

C were also conrmed by N

2
adsorptiondesorption
isotherm as displayed in Fig. 2A. Adsorption of a gas by a
porous material can be described quantitatively by using an
adsorptiondesorption isotherm which is the amount of gas
adsorbed at a xed temperature by the porous material as a func-
tion of pressure. Depending on the nature of porous structure,
it gives six types of isotherm. A typical characteristic of type H1
hysteresis is observed for MS and ZnOMS samples with an inec-
tion at the P/P
0
>0.39 due to capillary condensation [11]. The H1
hysteresis, whose loop appears on the vertical portion of type IV
isotherm, is usually produced for mesoporous materials with cylin-
drical pores [13,15]. The BJH pore size distribution plot of MS and
ZnOMSsamples areshowninFig. 2B. Fromthegure, it is observed
that the pore size of the MS sample is decreased after 30%ZnOload-
ing inside the MS. The data of specic surface area, average pore
size and pore volume for MS and 30% ZnOMS sample are shown
in Table 1. The specic surface area of the MS samples is found to
be decreased on loading the ZnO inside the mesopores which indi-
cates the insertion of ZnO inside the mesopores. It also indicates
Fig. 5. Photoluminescence (PL) spectra of calcined mesoporous silica (MS), bulk
ZnO and ZnOMS samples for 2 and 30wt% of Zn loading. Excitation is made using
365 nmand emission lter was used as 390nm.
that pores are not completely blocked and have the access inside
the pores. The decrease in the pore volume and average pore size
of ZnOMS samples also supports the formation of ZnO inside the
pores of MS.
The morphology of the calcined MS and ZnOMS samples is
investigated using HR-TEM and depicted in Fig. 3. Calcined MS
in Fig. 3A shows uniform and well oriented hexagonal pores hav-
ing pore size of 3.3nm. The electron diffraction pattern shown
in the inset of Fig. 3A indicates the amorphous nature of meso-
porous silica. The TEM image of ZnOMS sample in Fig. 3B also
shows hexagonal pores. Interestingly, the electron diffraction pat-
tern showed in the inset additionally exhibits the diffraction spots
due to hexagonal ZnO. This clearly suggests the formation of ZnO
crystals. HR-TEMimage of ZnOMS sample (inset of Fig. 3B) taken
with beam direction perpendicular to the pores indicates well-
aligned hexagonal pores.
Diffuse reectance UVVis spectra of the mesoporous silica and
ZnOMS samples for different ZnO loading are shown in Fig. 4. The
calcined MS sample does not showany absorption peak. However,
the absorption peak centered at 365nm for all the ZnOMS sam-
ples suggest the presence of ZnO particles [29]. The nature of the
absorption spectra of ZnOMS samples is similar to the absorp-
tion for ZnOincorporated in ZSM-5 zeolitic material [22]. The wide
absorption band from300 to 365nmobserved in the ZnOMS sam-
ples might be due the formation of one-dimensional array inside
the mesoporous silica which is expected for such type of crystal
growth [13].
854 P.B. Lihitkar et al. / Materials Chemistry and Physics 133 (2012) 850856
The photoluminescence (PL) spectra of MS and ZnOMS sam-
ples at RT are illustrated in Fig. 5. All the samples were excited
with 365nm wavelength using emission lter of 390nm. For the
sake of clarity, the photoluminescence spectra of only 2% and
30% Zn loaded ZnOMS samples are shown here. The photolu-
minescence spectra of bulk ZnO and calcined MS are also shown
for the comparison. It can be seen that, the calcined MS shows
three peaks of emission at 412nm, 423nm and 471nm. The blue
emission band at 412nm can be attributed to the oxygen defects
present on the surface of the oxide material which is also present
in bulk ZnO. The emission band at 423nm in mesoporous silica is
reported earlier [13,30] and can be attributed to two coordinated
silicon centers. Oxygen molecules interact with the photoactive
sites, which reduce the original active sites viz. Si, Si to
newly formed peroxy free radicals ( SiO
2
) which are responsi-
ble for emission band at 423nm in calcined MS sample [30]. The
band at 471nmis associated with oxygen anion vacancies created
at interface. All the Zn loaded mesoporous silica samples show
four bands of emission at 393nm, 412nm, 423nm and 471nm.
Almost similar emission bands are also observed by Jiang et al.
[13].
The 412nmand 423nmemission bands are present in ZnOMS
samples associated with the contributions fromthe oxygen vacan-
cies at the ZnOSiO
2
interface traps as well as from mesoporous
silica MS, which is also reported in ZnO/SBA-15 composites. The
emission peak at 393nm in ZnOMS samples is associated with
charge transitions due to Zn
2+
ions which is absent in the calcined
MS sample. At the highest Zn content (30% Zn) emission band at
393nmis broadenedwhichcanbe correlatedwiththe more defects
Fig. 6. Fourier transforms infrared (FTIR) spectra of calcined MS and ZnOMS sam-
ples having different weight percent of Zn loading.
onthe surface due tolarge amount of Znloading. The emissionband
at 393nm is attributed to the intrinsic emission of ZnO nanocrys-
talites [13] whichis also observed incase of bulk ZnO. However, the
PL band observed by Chen et al. [14] at 393nmis mostly attributed
to the radiative transition between electron (in conduction band)
and hole (in valence band) during the recombination process. The
emission at 405nmdue to ZnO nanoparticles conned in MCM-41
is alsoreportedusing 330nmexcitationwavelengths byXiong et al.
[17].
The bonding interactions between the host MS and guest ZnO
nanocrystals intheZnOMSnanocomposites areinvestigatedusing
FTIRspectroscopy andare showninFig. 6. The FTIRspectrumof cal-
cined MS is also shown in the gure for the comparison. A peak at
3257cm
1
in MS due to SiOH vibrations is found to be shifted to
3433cm
1
inZnOMSsamples (Table2). Theshift inOHvibrations
can be due to the presence of ZnOH over the surface of silica wall.
It is observed that, the peak at 974cm
1
is broadened and shifted
to 962cm
1
in ZnOMS samples on increasing the Zn content with
respect tocalcinedMS. Apeakat 974cm
1
gets broadenedinhigher
Zn content (30% Zn loading) of ZnOMS sample due to the pertur-
bation of Zn. This gives the evidence of ZnOSi bond formation
[13,16,17].
ZnO exhibits two IR absorption peaks at 512 and 496cm
1
,
while MS possesses three IR peaks of absorption around 960, 800
and 465cm
1
[13]. The decrease in the intensity and broadening
of the peak at 455cm
1
into doublet 465 and 430cm
1
is also
Fig. 7. X-ray photoelectron spectroscopy survey scan for (A) calcined mesoporous
silica and (B) ZnOmesoporous silica (30% Zn loading).
P.B. Lihitkar et al. / Materials Chemistry and Physics 133 (2012) 850856 855
Table 2
FTIR vibrations of calcined MS and ZnOMS for 30% Zn loaded sample.
Calcined MS peaks (cm
1
) Assignment ZnOMS peaks (cm
1
) Assignment Comments
3257 OH stretching 3433 OH stretching Shifted
1860 Si(OH)
2
1860 Disappeared
1624 SiOH 1630 ZnOH Shifted
1083 SiOSi symstretching 1058 SiOSi stretching Shifted
974 Bending SiOH 962 SiOZn Broadened and shifted
803 SiOSi 803 SiOSi Decreased in intensity
455 SiOSi 465, 430 ZnOSi Doublet
evident as a perturbation of SiOSi network due to the presence
of ZnO nanoparticles and can be assigned to ZnO bond in the ZnO
nanoparticles. The observed peak shifts and their assignments are
listed in Table 2.
Further, a peakat 803cm
1
associatedwithSiOSi stretchingis
found to be decreased on increasing the Zn content, which suggests
the perturbation of silica network due to ZnOSi interaction.
Insupport withtheFTIRspectroscopy, the MS andZnOMSsam-
ples were also investigated by solid state
29
Si NMR spectroscopy
to know the bonding interaction. The
29
Si NMR spectra of MS
and ZnOMS samples are shown in supporting information. We
observedthreechemical shifts inthespectrumfor ZnOMSsamples
at three different positions 92ppm, 101ppmand 109ppm. The
rst chemical shift at 92ppmis due to (SiO)
2
Si(OH)
2
Q2, second
Fig. 8. Detailed XPS spectra for (A) O1s of calcined MS, (B) O1s for ZnOMS sample and (C) Zn2p of ZnOMS sample for 30% Zn loading.
856 P.B. Lihitkar et al. / Materials Chemistry and Physics 133 (2012) 850856
chemical shift at 101ppmis due to (SiO)
3
SiOHQ3 where as third
chemical shift at 109ppmis associated with (SiO)
4
SiQ4 [24,31].
Achemical shift due toQ2andQ3is more prominent inthe ZnOMS
samples where as MS shows only Q1 chemical shift suggesting the
presence of ZnOSi bonding in the ZnOMS samples.
Additional conrmation of presence of ZnO comes from X-ray
photoelectron spectroscopy. X-ray photoelectron spectra of cal-
cined MS sample and ZnOMS (30% Zn) are illustrated in Fig. 7A
and B respectively. In Fig. 7A, presence of Si and O is noted. Sur-
vey scan of ZnOMS indicates that only Si, Zn, O and C elements
are present and no other impurity except carbon is present in the
sample. All the binding energies were corrected with reference to
the carbon 1s binding energy position at 285.0eV.
The detailed scan of O1s signal in MS and ZnOMS samples and
Zn2p signal in ZnOMS sample are shown in Fig. 8. The O1s sig-
nal of the calcined MS (Fig. 8A) shows a symmetric peak centered
at 532.6eV conrming the presence of O
2
(bonded to silicon) in
the sample and is close to the values reported earlier [7]. Decon-
volution of O1s XPS spectra for ZnOMS can be made using three
components (Fig. 8B). Thecalculatedbindingenergies of thesecom-
ponents are 532.8eV, 531.6eV and 530.0eV. The peaks at 531.6eV
and 530.0eV are due to the O1s for ZnO. The observed binding
energy is in well accordance with the values reported (i.e. 531.6eV
and 530.1eV) by Dupin et al. [32]. They have proposed the exis-
tence of two different oxygen species; one relates to the oxygen in
crystalline network (530.1eV) and the other due to the deciencies
on ZnO surfaces (531.6eV).
Additional peaks attributed to the weakly adsorbed species
wouldappear inthe range of 532533eV. Peak obtainedat 532.8eV
can be associated with weakly bound OH

or water molecules
adsorbed on the ZnO surface. Zn2p region of ZnOMS sample for
30% Zn content is shown in Fig. 8C. The binding energy for Zn2p
3/2
and Zn2p
1/2
at 1022.2eV and 1045.3eV respectively give a spin
orbit splitting (SOS) of 23.1eV. The binding energy observed at
1022.1eVby Fernandez et al. [25] is associated withbulk ZnO. Chen
et al. [14] have also observed the binding energy for Zn2p
3/2
peak at
1022.2eV and conclude the appearance of ZnO instead of chelated
zinc ions. SOS is sensitive to the chemical environment. There-
fore, in Zn metal it is 24.6eV but 22.2eV in pure ZnO [33]. Here,
in ZnOMS sample, it is 23.1eV which implies that the ZnOMS
material is not having pure ZnO but ZnO nanoparticles bonded to
SiO
2
surface of MS.
4. Conclusions
In summary, we have synthesized ordered mesoporous silica
with ZnO nanoparticles inside it. XRD analysis as well as TEM
analysis shows the presence of mesoporous structure. Electron
diffraction pattern as well as XPS conrm the presence of ZnO in
the ZnOMS samples. Decrease in the specic surface area, pore
volume and pore size of ZnOMS sample gives the strong evi-
dence of formation of ZnO inside the pores of mesoporous silica.
UVVis absorption and PL spectra also support the formation of
ZnO nanoparticles.
Acknowledgements
P.B.L. would like to thank Department of Science and Tech-
nology (DST), Govt. of India for the fellowship. S.K.K. would
like to thank University Grant Commission (UGC) for constant
support.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.matchemphys.2012.01.106.
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