Indian Journal of Pure & Applied Physics

Vol. 54, August 2016, pp. 485-488

Novel sol-gel method of synthesis of pure and aluminum doped TiO2

nanoparticles
Kirti Sahu* & V V S Murty
Department of Physics, Government Holkar Science College, Indore 452 017, India
Received 2 February 2016; revised 28 April 2016; accepted 10 June 2016

Pure and doped titanium dioxide (TiO2) nano particles have been prepared using acid tailored novel sol-gel method
based on the use of new chemicals using different doping concentration of metal aluminum (Al) at annealing temperature of
450 °C. Powder XRD and UV-Vis have been used to investigate the effect of Al doping in pure TiO2. Particle size analysis
using X-ray line broadening shows marginally increasing trend with increasing Al impurity. Results show that all samples
prepared by this method having particle size in the range of 11 nm to 23.9 nm. UV-Vis analysis indicates decrease in energy
band gap due to Al doping which means there is a shift in the solar spectrum towards the lower wavelength region in case of
doped TiO2 and hence absorption is increased as compared to pure TiO2. Metal doping of Al enhances electrical
conductivity due to plasmonic effect and improves optical transparency of TiO2 semiconductor at a low cost. The value of
band gap for pure TiO2 is 3.1 eV and decreases to 2.8 eV for 0.03 mole % of Al in Pure TiO2. Versatile, cheap and easy
novel method has been reported for preparation of pure and doped TiO2 nano particles, which can be used for making photo
anode for solar cells.

Keywords: Sol-gel, Annealing, Energy band gap, Photo anode

1 Introduction Aluminum (Al) doping plays a vital role in increasing

The application of titanium dioxide in photo solar cell performance in a cost effective manner. To
catalysis has been drawing increasing scientific increase light harvesting using dye sensitized solar
interest over recent years and many studies have cells (DSSCs), surface plasmon resonance effect of
focused on enhancing the performance of Titanium metal nanoparticles may be incorporated in photo
dioxide (TiO2) photo catalysts. TiO2 is widely used as anode. Results show that these metal nanoparticles
a pigment, as a catalyst support, and as a photo may localize the incident light and extend optical path
catalyst. In essence, the enhancement of the activity length in DSSCs for the improved performance20-22.
of TiO2 photo catalysts is attempted through the
enhancement of exciton generation, and/or the 2 Experimental
reduction of exciton recombination. Dopant elements 2.1 Materials
can be added to TiO2 to achieve various outcomes like This novel method is used to prepare pure and
formation of new valence states1-4 in TiO2, creation of doped TiO2 nanoparticle. Chemical reagents for the
charge carrier trapping sites5-8, band gap reduction9-11, preparation of pure and doped TiO2 nanoparticles
control of phase transformation behavior12-15 and used in this method are titanium tetra isopropoxide
surface area enhancement16. (TTIP) (Sigma-Aldrich), ethanol (Merck) and
It was usually found that different routes for doping hydrochloric acid (Hal) (Merck) Al2NO3, deionized
of metal in TiO2 often produce different results17-19. water, glacial acetic acid and anhydrous ethanol.
So it is necessary to investigate in detail the methods 2.2 Preparation of TiO2 nano powder
which may have important effect upon the particle In this typical method TiO2 nanoparticles are
size with proper doping. Doping of metal ions in TiO2 prepared using TTIP as raw material. Firstly, 20 mL
is the area of research for the scientist and ethanol was taken in a beaker and then 0.5 mL
researchers. One of the significant applications of this concentrated HCl acid was added slowly. This
doping is the solar cells with plasmonic effect. solution was manually stirred for half an hour. After
————— that 2.5 mL TTIP was added to this solution and
*Corresponding author (E-mail: [email protected]) stirred it for 2 h using magnetic stirrer in a sufficiently
486 INDIAN J PURE & APPL PHYS, VOL 54, AUGUST 2016

large beaker. Finally, this solution was kept for drying positions of pure TiO2 (tetragonal) in anatase form are
in hot air oven for 12 h at 100 °C. Obtained solids 25.4, 37.8, 48.2, 54.1 and 62.8 are in accordance with
were grounded well in agate mortar for 15 min and the reported value available in literature. Doping of Al
then kept for calcinations in muffle furnace at 450 °C in TiO2 thin film matrix is done by varying the
for 1 h. concentration of Al in pure TiO2. For successful
incorporation of Al in TiO2 and hence for enhanced
2.3 Preparation of doped TiO2 nano powder performance due to doping, there should be matching
In a typical method Al2NO3 (0.01, 0.03, 0.05 mole of ionic radii of Al and TiO2 ions up to a suitable
%) (Table 1) was dissolved in 60 mL of deionized level, then only doping is considered efficient and
water at room temperature followed by adding 5 mL would provide required results. Hence, results
of glacial acetic acid to obtain solution A. Titanium showing Al doping in TiO2 with 0.03 mole % has
isopropoxide (14 mL) was dissolved in 40 mL of particle size comparable to the size of pure TiO2
anhydrous ethanol with constant stirring to form nanoparticles indicating a suitable concentration of Al
solution B. Then solution B was added drop wise into in TiO2.
solution A within 60 min under vigorous stirring. XRD results are not showing any trend (increasing
Subsequently the obtained solution was stirred or decreasing) in the particle size with the
continuously for 2 h and aged for 24 h at room concentration variation of Al. Basically concentration
temperature. As prepared TiO2 gels were dried for 10 determines the photo catalytic activity of doped TiO2.
h at 80 °C. The obtained solids were ground and High concentration leads to high density of Al in TiO2
finally annealed at 450 °C for 2 h (heating rate=30
°C/min).

3 Results and Discussion

3.1 Crystal phase and particle size
Figure 1(a) and (b) shows the XRD patterns of the
samples prepared at annealing temperature of 450 °C.
Pure TiO2 nanoparticles prepared by this method can
be assigned to anatase crystal phase according to the
standards available in JCPDS (pattern No. 21-1272).
The results show that surface modified TiO2 possess
consistent peak positions and intensities with the
standard anatase TiO2. The average grain size is
calculated 25.20 from the main peak corresponding to
the [101] plane in the XRD pattern of anatase phase
of TiO2 using Scherer’s equation, i.e.:
௞λ
D = ஒୡ୭ୱø … (1)

where k is the constant for shape factor equal to 0.9, λ

is the X-ray wavelength, β is the full width at half
maximum of the peak and ø is the diffraction angle23.
Results show that particle size of the pure TiO2
sample with anatase phase is 11 nm. The peak
Table 1 — Particle size of undoped and doped TiO2 (Tetragonal)
Sample Mole % Al Grain size (nm)
Pure TiO2 0 11
Al doped TiO2 0.01 12.9
Al doped TiO2 0.03 11.2
Al doped TiO2 0.05 19.5 Fig. 1 — (a) XRD pattern of pure TiO2 and (b) XRD patterns of
Al doped TiO2 0.07 23.9 Al doped TiO2
 SAHU & MURTY: SYNTHESIS OF PURE AND ALUMINUM DOPED TiO2 487

UV-Vis diffuse reflectance spectra of the Al doped

TiO2, based on Kubelka–Munk function24:
(ଵିோ)మ ௞
F(R) = =ௌ … (2)
ଶோ

is observed in the wavelength range of 200–800 nm.

Here F(R) and R are the absorbance and the
reflectance of the samples, respectively. The
absorption properties and the band gap of materials
are calculated by using absorption spectra. The optical
band gap of the nanoparticles was determined by
using the Taut relation25:
αhν = β(hν–Eg)n … (3)
The value of n = 1/2, 3/2, 2 or 3 depending on the
nature of the electronic transition responsible for
absorption. Here n = 2 is used for indirect band gap
semiconductor26. Here α is Absorption coefficient, h
is Planck’s constant and ν is the photon frequency.
The indirect band gap value reported corresponding to
n = 2 in literature for bulk anatase is estimated from
3.10 to 3.20 eV. For pure and Al doped TiO2 samples,
Fig. 2(a) and 2(b) are illustrating the reflectance
absorbance and energy band gap respectively. Sample
doped with 0.03 mole % of Al showing a band gap
reduction from 3.1 eV to 2.83 eV. The change in band
gap with doping causes a spectral shift from UV
region to visible (blue) region.

Fig. 2 — (a) Reflectance vs wavelength curves and (b) Tauc plot 4 Conclusions
of pure and Al doped TiO2 Pure and Al doped TiO2 samples are prepared
successfully for the photocurrent enhancement using
resulting decrease in specific surface area available novel acid tailored sol-gel method. Band gap
for absorption due to agglomeration of particles. reduction of TiO2 is observed with appropriate
Nevertheless low density due to low concentration, concentration of Al in TiO2 and suitable particle size.
results minimum scattering causing decrease in XRD results shows that the particle size of TiO2 is
Plasmonic effect. purely in anatase form and from UV–Vis analysis
3.2 UV-Vis analysis results confirm that the doping of Al in TiO2 can
Electric method for band gap calculation using reduce the energy band gap of TiO2.
thermal excitation is not very useful as compared to
the optical method, which is very simple way of Acknowledgement
finding band gap. Energy band gap of pure and 0.03 Authors are greatly thankful to, K N Chaturvedi
mole percentage Al doped TiO2 are 3.1 eV and 2.8 Government Holkar Science College, Indore for
eV, respectively, which means there is a shift in the providing the laboratory facilities, V Ganeshan,
solar spectrum towards the lower wavelength region Mukul Gupta and Shilpa Tripathi, researchers UGC-
in case of doped TiO2 due to which absorption DAE-Consortium for Scientific Research for their
increases as compared to pure TiO2. Al doping in support in characterization of the samples and useful
suitable concentration induces energy levels in the discussions.
band gap of pure TiO2 just above the valence band of References
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