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Research Article

Received: 2 February 2010 Revised: 31 March 2010 Accepted: 7 April 2010 Published online in Wiley Interscience: 6 May 2010

(www.interscience.wiley.com) DOI 10.1002/sia.3558

Bandgap determination and charge separation


in Ag@TiO2 core shell nanoparticle films†
Ilknur Tunc,a Michael Bruns,c Hartmut Gliemann,d Michael Grunzea
and Patrick Koelsch,a,b∗
The photocatalytic activity of TiO2 under sunlight irradiation depends on the bandgap energy. Due to the relatively low
solar intensity in the UV region (<10%) and the fact that the bandgap of TiO2 is usually greater than 3 eV (below 400 nm),
many attempts have been made to shift the bandgap towards lower energies. Here, we investigate the structure, chemical
composition, bandgap shift and charge transfer processes of Ag@TiO2 core-shell nanoparticle thin films by field emission
scanning electron microscopy, atomic force microscopy, XPS, and UV-Vis spectroscopy. As a solid support, Au-coated Si wafers
and Si surface covered with a native oxide were used and homogenously covered by Ag@TiO2 core-shell nanoparticles with
overall film thicknesses of 80–100 nm and size distributions between 8 and 15 nm. The shell thickness of the adsorbed Ag@TiO2
particles was estimated to be 1.5-2.0 nm. The effect of the Ag core on the bandgap of TiO2 and photoinduced charge separation
of Ag@TiO2 nanoparticle films was studied by UV-Vis reflectance spectroscopy using the Kubelka-Munk formalism. Films of
Ag@TiO2 core-shell nanoparticles revealed a substantially reduced bandgap of 2.75 eV (corresponding to 450 nm), and an
electron charge transfer to the Ag core occurring upon UV irradiation on nonconductive surfaces. These features make Ag@TiO2
particulate films a promising candidate for photocatalytic surfaces under sunlight irradiation. Copyright c 2010 John Wiley &
Sons, Ltd.

Keywords: core-shell nanoparticles; photocatalytic activity; TiO2 ; bandgap; charge separation

Introduction the reflectance into the equivalent absorption coefficient. A plot


of the Kubelka–Munk equivalent absorption coefficient versus the
TiO2 has been studied widely as the photocatalyst for organic photon energy is then usually used to evaluate the corresponding
synthesis[1 – 4] and for environmental cleaning processes.[5 – 7] bandgap energy.[13 – 14] Here, we have applied this formalism to
Recently, applications on photocatalysis and photoactivity of estimate the bandgap of Ag@TiO2 core-shell nanoparticles, a
TiO2 as a material have included antifouling,[8] antibacterial,[9] quantity which so far has not been reported in literature.
deodorizing[10] and self-cleaning functions.[11] In close connection Another issue which determines the photocatalytic activity
with the developments in academic research, TiO2 photocatalysis is the suppression of e-h recombination. Decoration of TiO2
technology has also become more and more attractive to industry, nanoparticles with metals show reduced e-h pair recombination
since it is an effective, easily available, relatively inexpensive and rates due to the transfer of the photogenerated electrons to
chemically stable material, and has many promising applications in the metal surfaces.[12,15 – 17] In addition to these studies, we
combating the rise of global environmental pollution and related investigated charge transfer processes of Ag@TiO2 nanoparticle
phenomena. films on conducting and nonconducting surfaces.
The bandgap of TiO2 determines the energy necessary to The purposes of this article are: (i) to characterize uniform
create electron-hole (e-h) pairs in the semiconductor to innervate Ag@TiO2 nanoparticle thin films on gold and silicon surfaces by
photocatalytic processes. Au and Ag nanocomposits with TiO2 UV-Vis Spectroscopy, transmission electron spectroscopy (TEM),
particles as well as metal/TiO2 core-shell nanoparticles are
assumed to change the bandgap properties. Fig. 1 shows the
transmission UV-Vis spectra of TiO2 nanoparticles (black curve), Ag

nanoparticles (yellow curve), and Ag@TiO2 core shell nanoparticles Correspondence to: Patrick Koelsch, Applied Physical Chemistry, Heidelberg
University, Im Neuenheimer Feld 253, 69120 Heidelberg, Germany.
(brown curve) in ethanol solution. The bandgap for TiO2 can be E-mail: patrick.koelsch@kit.edu
estimated from the absorption onset to be around 3.7 eV, however,
the overlap between the bandgap absorption and the surface † Paper published as part of the ECASIA 2009 special issue.
plasmon resonance (SPR) band of the Ag core in the Ag@TiO2
a Applied Physical Chemistry, University Heidelberg, 69120 Heidelberg, Germany
transmission UV-Vis spectra makes it impossible to evaluate the
bandgap from the solution spectra. Also note, that the SPR band b Genetics, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1,
of citrate-capped Ag nanoparticles is around 395 nm, whereas the 76344 Eggenstein-Leopoldshafen, Germany
one relating to Ag@TiO2 is considerably red-shifted at 470 nm
related to the higher refractive index of the titania shell.[12] c Materials Research III, Karlsruhe Institute of Technology, Hermannvon-
Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany
A useful alternative to solution studies is the investigation of thin
particulate films by UV-Vis reflectance spectroscopy. This allows d Institute of Functional Interfaces, Karlsruhe Institute of Technology, Hermann-
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the application of the Kubelka–Munk formalism which converts von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany

Surf. Interface Anal. 2010, 42, 835–841 Copyright 


c 2010 John Wiley & Sons, Ltd.
I. Tunc et al.

nanoparticle layers.[19] However, in this case the PAA poly-


electrolyte layers interfere during the photocatalytic applica-
tion. Therefore, we prepared thin particulate films by dropping
100–150 μl particle solution onto a clean CVD-deposited 100 nm
Au film on a Si wafer and on a bare Si wafer (1 cm × 1.5 cm) and
dried at room temperature in a closed petri dish.

Methods
The UV-Vis absorption and reflection spectra were recorded
using a Varian CARY 500 Scan UV-Vis-NIR and an Ocean-Optics
HR2000 spectrophotometer, respectively. In order to probe the
bandgap, reflectance data were reported and equivalent bandgap
determinations were made by plotting [F(R∞) × hν]1/2 versus hν
(eV) by Kubelka-Munk theory using the corresponding reflectance
data (results section).[13] A 47 W Hg-lamp (model TQ-150) was
Figure 1. UV-Vis Absorption Spectra of Ag@TiO2 , pure Ag and TiO2 colloids. used for UV-irradiation. All these measurements were performed
Inset shows the color of the corresponding colloids. at room temperature.
A Multimode AFM operated with a Nanoscope IIIa controller
(Digital Instruments) was used for the investigation of the
atomic force microscopy (AFM), field-emission scanning electron particles on the substrates. The AFM was operated in air at
microscopy (FE-SEM), and detailed XPS; (ii) to study the effect room temperature in intermittent contact mode. Bar-shaped Si
of the Ag core on the bandgap of TiO2 ; and (iii) to investigate cantilevers (Nanosensors) with typical force constants between 30
the photoinduced charge separation upon UV-irradiation in TiO2 and 70 N/m were used.
when Ag@TiO2 nanoparticles are deposited uniformly on different XPS measurements were performed using a K-Alpha XPS
substrates. spectrometer (ThermoFisher Scientific, East Grinstead, UK). Data
acquisition and processing using the Thermo Avantage software is
described elsewhere.[20] All nanoparticle thin films were analyzed
Experimental using a microfocused, monochromated Al Kα X-ray source
(30–400 μm spot size). The K-Alpha charge compensation system
Materials
was employed during analysis, using electrons of 8 eV energy,
Titanium-(triethanolaminato)isopropoxide(N(CH2 )2 O)3 -TiOCH and low-energy argon ions to prevent any localized charge build-
(CH3 )2 ) (TTEAIP), dimethylformamide (DMF), AgNO3 , isopro- up. Sputter depth profiles were performed using 1000 eV Ar+
popanol and ethanol were purchased from Sigma-Aldrich and ions. The spectra were fitted with one or more Voigt profiles (BE
used as received. Ag@TiO2 nanoparticles were prepared by the uncertainty: +0.2 eV) and Scofield sensitivity factors were applied
procedure reported by Kamat et al.[12] Briefly, 18 ml of TTEAIP for quantification.[21] All spectra were referenced to the C1s peak
solution in isoproponol (8.3 mM) was mixed with 2 ml AgNO3 assumed to originate from surface hydrocarbon contamination at
aqeous solution (15 mM). DMF in the amount of 10 ml was then 285.0 eV binding energy, and for comparison to the Au 4f7/2 peak
added as a reducing agent to the mixed solution. The concentra- at 84.0 eV, respectively.
tion of Ag+ ions and TTEAIP in the reaction mixture was 1 and 5 mM, FE-SEM investigations were performed in a Zeiss Supra 55
respectively. The mixed solution was stirred for 15 min and then scanning electron microscope (Carl Zeiss SMT AG, Oberkochen,
refluxed for 90 min. The color change from transparent to dark Germany) using a magnification up to 3 ×106 at 15 kV accelerating
brown within this period was evidence of the formation of Ag@TiO2 voltage.
nanoparticles. The reaction solution was then cooled down while HRTEM investigations were performed on a Tecnai F20-ST (FEI
continuing to be stirred. The colloids (30 ml) were centrifuged and Company, USA), operating at 200 keV. For TEM sample preparation
redispersed in 20 ml absolute ethanol to remove any unreacted nanoparticle-containing solutions were dropped on 300 mesh Cu
reagents. TiO2 colloids were prepared by the procedure similar to grids covered with holed carbon films. The solvent (ethanol) was
that for Ag@TiO2 nanoparticles except for the addition of AgNO3 evaporated before inserting the sample into the microscope.
solution. The slow hydrolysis of TTEAIP resulted in a transparent Current measurements between the Au surface and the
TiO2 nanoparticle solution. Particles were cleaned by centrifuga- Ag@TiO2 film was performed by clamping two electrodes on
tion, redispersed in ethanol and deposited on the Au coated wafer the Au and the nanoparticle film, respectively. The current was
by the method described above. Pure Ag nanoparticles were pre- measured using an electrometer (Keithley 614 Electrometer).
pared according to the previously published procedure.[18] In brief,
1 ml of 0.01 M AgNO3 aqueous solution was rapidly added to 99 ml
of aqueous solution containing 0.3 mM sodium-citrate and 1 mM Results and Discussion
NaBH4 under vigorous stirring at room temperature. The color of
the solution turned yellow in a few minutes, which indicates the Despite the fact that the transfer of particles out of the solution
formation of Ag nanoparticles. to the surface is an important issue related to the tendency
In order to deposit Ag@TiO2 particles onto the surface, Liz- to coalesce, the production of a well-defined uniform Ag@TiO2
Marzan et al. have used layer-by-layer deposition method us- particle film is vital for photocatalytic applications. Prior to the
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ing poly(acrylic acid) (PAA) polyelectrolytes between Ag@TiO2 functionality studies of the Ag@TiO2 core shell particles with

www.interscience.wiley.com/journal/sia Copyright 
c 2010 John Wiley & Sons, Ltd. Surf. Interface Anal. 2010, 42, 835–841
Bandgap determination and charge separation in Ag@TiO2

Figure 2. (A) AFM topography images of Ag@TiO2 deposited on Au coated wafer. (B) Si wafer, (scan area: 1 μm × 1 μm). (C) Field emission scanning
electron micrograph of a cross-section of Ag@TiO2 nanoparticle film deposited on 100 nm Au wafer.

respect to their optical properties, the resulting thin films were XPS is suitable to estimate the thickness of flat thin films.
comprehensively characterized by surface analytical methods. The description of the detailed underlying formalism based on a
AFM was used to investigate the topography of the freshly modified Lambert-Beer equation and least square fitting recently
prepared Ag@TiO2 core shell particle thin films and images are has been the subject of a series of comprehensive papers.[20,26,27]
shown for the gold and silicon substrates in Fig. 2 (A) and (B), In the case of Al (15 nm)core@Al2 O3 shell nanoparticles, J. C.
respectively. In both cases, the surface is homogenously covered Sánchez-López et al.[28] proved that an assumed cubic shape for
by particles with a comparable size distribution and density. The the particles, although not in close accordance to the observed
particle size is between 8 and 15 nm, which is in agreement with morphology, is a reasonable model for quantitative XPS analysis
TEM measurements (data not shown). Figure 2(C) shows an FE- for these samples. Therefore, the reported formalism was applied
SEM picture at the edge of the substrate. The measured thickness to the present Ag@TiO2 core shell nanoparticle films using Ti 2p3/2
of the film is around 80–100 nm and was comparable for Ag@TiO2 as the shell signal and Ag 3d5/2 as the core signal. Together with
particle films on Au and on Si, also in agreement with AFM thickness TEM results of the uncoated Ag nanoparticles revealing sizes of
measurements (data not shown). about 7–15 nm for the Ag core particles, the calculated TiO2 shell
thickness from the XPS measurements was found to be 1.5–2.0 nm.
In order to obtain information on chemical binding states of
The neglect of organic contaminants is justified by the fact that
the core/shell nanoparticle films and, together with AFM and
both Ag 3d5/2 and Ti 2p3/2 photoelectrons have almost the same
TEM data, to get an estimation of the TiO2 shell thickness,
inelastic mean free path in this material, leading to comparable
XPS measurements were conducted. Figure 3(A) shows the XPS
intensity attenuation.
spectrum corresponding to Ti2p3/2 and Ag3d5/2 regions. The
However, measurements and theoretical predictions of attenu-
binding energies measured for Ag (Ag 3d5/2 = 368.2 eV), TiO2
ation lengths may have large uncertainties (>6%).[23,25] Together
(Ti 2p3/2 = 458.9 eV and O 1s = 530.4 eV), and Ti2+/3+ (Ti with experimental uncertainties, one can expect an entire devia-
2p3/2 = 457.6 eV) as well as for organic contaminants are in tion of about 20%.
a good agreement with reference data and close to those UV-Vis spectra of TiO2 and Ag@TiO2 nanoparticle films de-
reported in the literature.[21 – 25] Fig. 3(B) shows the sputtering posited on an Au-coated Si wafer are shown in Fig. 4(A). The
depth profile upon Ar+ ion bombardment. The film thickness of band located at 465 nm is evidence for the presence of Ag@TiO2
the Ag@TiO2 nanoparticle film was again about 80 nm. In case nanoparticles on the Au surface. The slight 5 nm spectral shift
of the particle constituents, Ag and Ti sputter depth profiles compared to the SPR band shown in Fig. 1 may be due to a
show constant intensity ratios throughout the film, although a change of dielectricity of the enviroment as the nanoparticles are
significant amount of reduced Ti states has to be considered due deposited onto the Au surface.
to Ar+ ion bombardment.[25] The sputter depth profiles also show One of the major objectives of the incorporation of Ag into TiO2
an averaged carbon contamination of about 25% throughout nanoparticles is to increase the wavelength response range in or-
the particle film. This is probably due to incomplete removal of der to enhance the photoexcitation efficiency of TiO2 . Therefore,
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precursor material and/or solvent residuals. the bandgap of Ag@TiO2 and TiO2 nanoparticles were determined

Surf. Interface Anal. 2010, 42, 835–841 Copyright 


c 2010 John Wiley & Sons, Ltd. www.interscience.wiley.com/journal/sia
I. Tunc et al.

Figure 3. (A) The part of the XPS spectrum corresponding to Ti2p3/2 and
Ag3d5/2 regions. (B) Sputter depth profile of Ag@TiO2 nanoparticle film
Figure 4. (A) UV-Vis Reflection Spectra of Ag@TiO2 nanoparticles (showing
deposited onto an Au surface.
a maximum at 470 nm) and TiO2 nanoparticles films deposited on 100 nm
Au layer. (B) Bandgap determination using Kubelka-Munk Function ([F(R∞)
hυ]1/2 ) versus hυ plots (assuming indirect optical transition) for TiO2 and
by using the reflection UV-Vis spectra shown in Fig. 4(B). The Ag@TiO2 nanoparticles. The direction of the arrow indicates the bandgap
reflectance spectra were analyzed by means of the Kubelka–Munk shift by Ag modification.
formalism to convert the reflectance into the equivalent ab-
sorption coefficient, α, which is proportional to Kubelka–Munk
function F(R∞ ), given in the following equation:[13 – 14] 335 nm). This presents (i) that studying thin films of Ag@TiO2
nanoparticles allows the determination of the bandgap, even
(1 − R∞ )2 K when it is overlapped with the SPR band, and (ii) reveals the
F(R∞ ) = = (1) potential of Ag@TiO2 core-shell nanoparticle films as promising
2R∞ S
candidate for novel and more efficient photoprocessors as the
where, R∞ of a powder is the measured absolute reflectance from bandgap is significantly shifted to the visible region.
an infinitely thick layer of sample (R∞ = Rsample /Rstandard ), K is If a metal gets in contact with a semiconductor, the Fermi
the absorption coefficient, and S is the scattering coefficient for a levels of the two systems equilibrate in such a way that it shifts
given wavelength. The bandgap can be obtained from the plots close to the conduction band (CB) of the semiconductor.[29] Due
of [F(R∞ )hυ]1/2 versus hυ, as the intercept of the extrapolated to this readjustment the energy levels bent to higher energies
linear part of the plot at [F(R∞ )hυ]1/2 = 0, assuming that the forming a Schottky barrier for the trapped electrons (see scheme 1
absorption coefficient α is proportional to the Kubelka–Munk a and b).[30] To further investigate charge separation in core-
function F(R∞ ) (Fig. 4(B)). The presence of a clearly identifiable shell nanoparticles, UV-Vis spectra of Ag@TiO2 nanoparticles in
band-edge absorption feature is present in both datasets, showing ethanol solution and particles deposited on gold and silicon
that the Kubelka-Munk formalism works for both, the TiO2 and the surfaces were recorded before and after UV-illumination. The SPR
Ag@TiO2 films. Correspondingly, the absorption edge of Ag@TiO2 band for Ag@TiO2 nanoparticles in ethanol solution before UV-
nanoparticles (2.75 eV; 450 nm) shifts significantly to the visible irradiation was observed at 470 nm (Fig. 5(A)). When the colloids
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range, compared to that of pure TiO2 nanoparticles (3.7 eV; were subjected to 10 min UV-irradiation, the position of the SPR

www.interscience.wiley.com/journal/sia Copyright 
c 2010 John Wiley & Sons, Ltd. Surf. Interface Anal. 2010, 42, 835–841
Bandgap determination and charge separation in Ag@TiO2

Scheme 2. Schematic Illustration of the experimental set up for the current


measurement.

Fig. 5(B) displays the reflection band of Ag@TiO2 nanoparti-


cles deposited on the Au surface before and after UV irradiation.
As clearly seen from the figure, no spectral shift is recorded af-
ter subjecting Ag@TiO2 film to UV illumination. As a result, two
possible states can be achieved: i) the electron transfer men-
tioned above does not take place when Ag@TiO2 nanoparticles
are deposited onto the Au surface or, ii) electron transfer takes
places through the Au surface instead of the Ag core. To fur-
ther investigate these scenaris, the charging of the sample was
measured by clamping electrodes on the Au surface and the
Ag@TiO2 nanoparticle film (Scheme 2). Around 15 μA current was
measured during UV irradiation, indicating that electron tranfer
Scheme 1. (a) Charge distribution between TiO2 and Ag core. EF and takes place from the TiO2 shell to the Au surface and not to the Ag
EF  refer to Fermi levels of TiO2 before and after attaining equilibrium, core.
respectively. (b) schematic presentation of the Schottky barrier.
This is related to the fact that both the gas-phase electron
affinity and the ionization potential of small clusters of the same
band shifted to 430 nm. This large blue-shift is a result of an size are higher for Au than for Ag.[33] When the ionization energies
increased electron density in the Ag core during photoirradiation. and electron affinities in the gaseous phase are extrapolated to
There are two major factors affecting the SPR band of metal the solid state, it is expected that the Au surface is better and
clusters, namely the dielectricity of the surrounding medium and faster at capturing electrons, in agreement with our findings. In
the density of the metal clusters electrons. Accordingly, the bulk the next step, Ag@TiO2 nanoparticles were deposited on a Si
plasmon frequency of metal particles ωp is proportional to the surface covered with a native oxide. A spectral shift similar to
square root of electron density (n) in the particles and inversely that observed in solution (Fig. 1) was recorded by subjecting the
proportional to the square root of effective mass (meff ) and vacuum Ag@TiO2 film to UV illumination, as seen in Fig. 5(C). In this case,
permittivity (ε0 ), as shown by the following equation:[31] photogenerated electrons transfer to the Ag core, since there is
no way for them to be captured by the Si surface. As expected,
ne2 there was no current flow recorded between Si surface and the
ωp2 = (2) Ag@TiO2 nanoparticle film.
ε0 meff

Hence, additional electrons in the Ag core are expected to lead


to a blue-shift in the spectrum, a result which has previously been Conclusion
shown by correlating the extent of the band shift with the electron
density around Ag particles irradiated by UV light.[12,16,32] In the We have produced uniform films of Ag@TiO2 core-shell nanopar-
case of Ag@TiO2 particles, electrons generated in the excitation ticles on Au and Si substrates. The bandgap measured for these
process transfer to the Ag core, while holes are scavenged by films shifts by 115 nm more to the visible regime in comparison to
ethanol. TiO2 nanoparticles of the same size. The photoinduced electron
As Ag has a favorable Fermi energy (EF = 0.4 V), one can expect transfer towards Ag core, as a result of charge separation upon
a facile electron transfer from excited TiO2 to the Ag core: UV-irradiation in TiO2 , takes place not only in the solution but also
when Ag@TiO2 nanoparticles are deposited uniformly on non-
(3) conducting substrates. For the first time we have demonstrated
TiO2 TiO2(e+h)
the photoinduced charge transfer on surfaces and demonstrated
TiO2(h) + ethanol products (4) the potential ability of this material as a photocatalyst in surface
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TiO2(e) + Ag TiO2+ Ag(e) (5) applications requiring sunlight activation.

Surf. Interface Anal. 2010, 42, 835–841 Copyright 


c 2010 John Wiley & Sons, Ltd. www.interscience.wiley.com/journal/sia
I. Tunc et al.

Figure 5. (A) UV-Vis Absorption Spectra Ag@TiO2 nanoparticles in ethanolic solution recorded before and after 10 min UV-illumination. The direction of
the arrow indicates the spectral shift upon UV-irradiation. (B) Reflection Spectra of Ag@TiO2 nanoparticles on 100 nm Au layer before and after 10 min
UV-radiation. The dotted line implies no spectral shift upon UV-radiation. (C) Reflection Spectra of Ag@TiO2 nanoparticles on Si surface before and after
10 min UV-radiation. The direction of the arrow implies spectral shift upon UV-radiation.

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