Accepted Manuscript

Effect of alcohol solvents on TiO2 films prepared by sol–gel

method

Orawan Wiranwetchayan, Surin Promnopas, Titipun Thongtem,

Arnon Chaipanich, Somchai Thongtem

PII: S0257-8972(17)30770-3
DOI: doi: 10.1016/j.surfcoat.2017.07.068
Reference: SCT 22554
To appear in: Surface & Coatings Technology
Received date: 30 January 2017
Revised date: 29 June 2017
Accepted date: 29 July 2017

Please cite this article as: Orawan Wiranwetchayan, Surin Promnopas, Titipun Thongtem,
Arnon Chaipanich, Somchai Thongtem , Effect of alcohol solvents on TiO2 films prepared
by sol–gel method, Surface & Coatings Technology (2017), doi: 10.1016/
j.surfcoat.2017.07.068

This is a PDF file of an unedited manuscript that has been accepted for publication. As
a service to our customers we are providing this early version of the manuscript. The
manuscript will undergo copyediting, typesetting, and review of the resulting proof before
it is published in its final form. Please note that during the production process errors may
be discovered which could affect the content, and all legal disclaimers that apply to the
journal pertain.
 ACCEPTED MANUSCRIPT
1

Effect of alcohol solvents on TiO2 films prepared by sol–gel method

Orawan Wiranwetchayan1,*, Surin Promnopas1, Titipun Thongtem2,3,

Arnon Chaipanich1,3 and Somchai Thongtem1,3
1
Department of Physics and Materials Science, Faculty of Science,
Chiang Mai University, Chiang Mai 50200, Thailand
2
Department of Chemistry, Faculty of Science, Chiang Mai University,
Chiang Mai 50200, Thailand

PT
3
Materials Science Research Center, Faculty of Science, Chiang Mai University,
Chiang Mai 50200, Thailand

RI
SC
Corresponding author: wiranwetchayan@gmail.com (O. Wiranwetchayan)
NU
Abstract
The TiO2 (anatase) films were prepared by sol-gel method using titanium (IV)
isopropoxide (TTIP) as a precursor and polyvinylpyrrolidone (PVP) as a polymeric
MA

precursor dissolved in different alcohol solvents (methanol, ethanol, isopropanol and

1-butanol) and were heated treatment at 450 oC for 1 h. In this research, the alcohol
D

solvents have significant influence on the morphology, crystalline degree and energy
band gap of TiO2. The number of carbon, boiling point, dielectric constant and
E

viscosity of alcohol solvents were the main factor influencing the size of TiO2
PT

nanoparticles. The alcohol solvent with higher boiling point and viscosity, and long
length of carbon chain can lead to the smaller crystallite size. The number of carbon
CE

and viscosity of solvent and crystallite size can play the important role in the
agglomeration of particles. The energy band gaps of the films determined by UV-
AC

visible spectroscopy were in the 3.00−3.30 eV range.

Keywords: TiO2 films; X-ray diffraction; Electron microscopy; Spectroscopy

1. Introduction
The primarily application of titanium dioxide (TiO2) has been used as a pigment
in paints, printing ink, cosmetics, soap, toothpaste, polymer and others in which
white coloration is required [1]. TiO2 occurs in three different polymorphs: rutile
(tetragonal), anatase (tetragonal) and brookite (orthorhombic) [2]. At present, TiO2
 ACCEPTED MANUSCRIPT
2

has been widely used in a number of applications such as photocatalysis [3, 4] dye-
sensitized solar cells [5–8], gas sensors [9–11], batteries [12–14], self-cleaning
glasses [15], stormwater disinfection [16] and production of hydrogen fuel [17, 18].
Thus, preparation of TiO2 film is the most important field of nanomaterials.
Several physical and chemical techniques such as sputtering [19, 20], chemical
vapor deposition (CVD) [21, 22], metal-organic chemical vapor deposition (MOCVD)
[23], spray pyrolysis [24], supersonic aerosol deposition [25], pulsed laser deposition
[26], sol-gel [27–30], hydrolysis [31, 32], hydrothermal [31] sparking [33] and

PT
microwave-assisted solvothermal [34] have been used for preparing of TiO2.
Moreover, the properties of TiO2 films, crystalline structure, surface area, size

RI
distribution, porosity and film thickness, are highly controlled by preparation

SC
methods. Among them, the sol-gel method is widely used because it requires low
temperature processing, large area coatings, simple and in-expensive. Thus, it is
NU
appropriate for fabrication of porous and homogeneous multicomponent oxide films
[30]. The sol-gel process involves conversion of monomers into a colloidal solution
(sol) acting as the precursor for an integrated network (gel) of either discrete
MA

particles or network polymer. Typical precursors are metal alkoxide. The final product
might have several structures by controlling gelation condition: the precursor
D

hydrolysis, polycondensation, gel condensation and drying/calcination [35, 36]. The

titanium (IV) isopropoxide (TTIP) precursor has been frequently used to produce the
E

TiO2 film because TTIP is a suitable precursor with no toxic of by-products [37].
PT

In this research, the anatase TiO2 films were prepared on glass substrates by
sol-gel method in different alcohol solvents (methanol, ethanol, isopropanol and 1-
CE

butanol), with TTIP as a precursor and PVP as a polymeric precursor. The influences
of alcohol solvents with different carbon numbers, boiling points, viscosity and
AC

dielectric constant on the crystalline structure, morphology and energy band gap of
TiO2 were investigated and discussed.

2. Experimental procedure
2.1 Materials
Acetic acid (glacial) 100%, titanium (IV) isopropoxide 97% (TTIP,
Ti(OCH(CH3)2)4), polyvinylpyrrolidone (PVP, Mw = 360,000), 1-butanol (butan-1-ol,
CH3(CH2)3OH), ethanol 99% (C2H6O), methanol (CH3OH) and isopropanol (propan-
2-ol, C3H7OH) were used in this synthesis.
 ACCEPTED MANUSCRIPT
3

2.2 Preparation of TiO2 thin films

TiO2 films were fabricated by the sol–gel method in different alcohol solvents:
methanol, ethanol, isopropanol and 1-butanol. Two solutions were prepared: (Sol1)
0.75 ml of TTIP was dissolved in a solution of 1.5 ml of alcohol and 1.5 ml of acetic
acid with continuous magnetic stirring for 30 min. (Sol2) 0.3 g of PVP was added to
2.5 ml of alcohol solvent with 30 min stirring. The two solutions were mixed together
and vigorously stirred at room temperature for 120 min. In the end, the mixture was

PT
coated on the glass substrates by doctor blade method and followed by 450 oC heat
treatment for 1 h.

RI
SC
2.3 Characterization
Phase and structure of the films were characterized by X-ray diffraction (XRD,
NU
Rigaku MiniFlex™ II) operating at 20 kV and 15 mA using Cu-Kα line in combination
with the JCPDS database, Fourier transform infrared spectroscopy (FTIR, Bruker
Tensor 27) operating in the range of 400 – 4000 cm–1 and Raman spectrophotometry
MA

(T64000 HORIBA Jobin Yvon) using a 50 mW and 514.5 nm wavelength Ar green

laser. UV-visible spectra were examined by UV-visible spectroscopy (PerkinElmer
D

Lambda 25). Surface morphology of the TiO2 films was studied by field emission
scanning electron microscopy (FE-SEM, JEOL JSM-6335F) operating at 15 kV and
E

transmission electron microscopy (TEM, JEOL JEM-2010) operating at 200 kV.

PT

3. Results and discussion

CE

Effect of solvent on the properties of the TiO2 crystals was studied by

classifying the alcohol with different carbon numbers: methanol, ethanol, isopropanol
AC

and 1-butanol. Generally, the crystallization process plays a significant role in

defining the crystalline structure, shape and size of the TiO2 particles. The primary
particles nucleated from precursor solution by molecular addition or aggregation of
small subunits. The particle growth after nucleation was controlled by the alcoholic
solvents. The surface morphology of the as-prepared TiO2 films with different alcohol
solvents and annealed at 450 oC for 1 h were examined by FE-SEM, as the results
presented in Fig. 1. The surfaces of all TiO2 films were smooth and homogenous
without crack detection. The TiO2 films had strong adhesion with the glass
substrates. Those fabricated in methanol, ethanol and isopropanol contained large
 ACCEPTED MANUSCRIPT
4

spherical particles which were aggregated from primary particles to the larger ones.
But for the film fabricated in 1-butanol, the small particles clustered together in
colonies. The size of aggregated particles (secondary particles) characterized by
SEM is summarized in Table 1. The average diameters of the aggregate TiO2
particles were about 83 nm, 85 nm and 70 nm for those prepared in ethanol,
methanol and 1-butanol solvents, respectively.
A transmission electron microscopy was used to characterize morphology and
crystalline degree of the films. TEM bright field images and selected area electron

PT
diffraction (SAED) patterns of TiO2 prepared in different solvents are displayed in Fig.
2. Clearly, the particles of films were mostly spherical shape with random distribution

RI
in different directions. The primary particle sizes were estimated to be ~13–16 nm.

SC
They should be noted that the alcohol solvents can lead to obtain nanoparticles.
These results indicated that PVP can play an important role in producing spherical
NU
nanoparticles. The corresponding SAED patterns (inset of Fig. 2) present five
diffraction rings. Calculated d-spaces and Miller indices of anatase TiO2 crystals
were compared with those of the JCPDS database no. 21-1272 [38] and were
MA

summarized in Table 2. They belonged to the (101), (004), (200), (211) and (204)
planes of the anatase phase (JCPDS database no. 21-1272) [38]. The high-
D

resolution TEM (HR-TEM) images of TiO2 nanoparticles are shown in Fig. 3. The
d-spacing values of the samples were ~0.35 nm and ~0.23 nm, corresponding to the
E

(101) and (004) lattice planes of the anatase TiO2. The information obtained from d-
PT

spacing values was in accordance with the above results of SAED analysis.
To further determine crystalline structure, XRD patterns of the samples
CE

produced in ethanol, methanol, 1-butanol and isopropanol solvents after heat

treatment at 450 oC for 1 h are shown in Fig. 4. The peaks at 2 of 25.3o, 37.8o,
AC

48.1o, 53.9o, 55.0o, 62.7o, 68.7o, 70.1o and 75.0o can be assigned to the (101), (004),
(200), (105), (211), (204), (116), (220) and (215) crystal planes of tetragonal anatase
phase (JCPDS database no. 21-1272), respectively [2–4, 38–40]. The XRD results
are in accordance with those of the SAED and HR-TEM analyses. Comparing the
relative height of intensity of the (101) peak at 2θ = 25.5o with those of other peaks,
there were the preferential growth direction of these products. Furthermore, XRD
analysis indicates that TiO2 is pure anatase (JCPDS no. 21-1272) [38], regardless of
the solvents used for preparing. The as-prepared films show the main peak almost at
 ACCEPTED MANUSCRIPT
5

the same position, caused by variation in defects of the films and alcohol solvents.
The intensity of main peak is also different, caused by the difference in crystalline
degree and crystallite size. Upon changing of alcohol solvents in sequence of
increasing boiling points (Tbmethanol = 64.7 oC, Tbethanol = 78.24 oC, Tbisopropanol = 82.6 oC
and Tb1-butanol = 117.7 oC), the films became to lessen the crystalline degree, and the
film produced in methanol is the best crystal.
The average crystallite size of TiO2 particles was calculated from the (101)
diffraction peak by the Scherrer formula

PT
(1)


RI
, where the shape factor K is 0.9, is the wavelength of Cu-K radiation (0.45106
nm), FWHM is full width at half maximum of the (101) peak and θ is the Bragg’s

SC
angle [41]. The crystallite size of TiO2 nanoparticles prepared in different alcohol
solvents are shown in Table 1. They were found to have slightly increase in size in
NU
sequence: 1-butanol (~ 9.3 nm) < isopropanol (~ 10.1 nm) < ethanol (~ 11.9 nm) <
methanol (~ 12.2 nm).
MA

The effects of solvent properties, such as viscosity, dielectric constant, boiling

point and number of carbons on the crystallite size were analyzed as follows.
According to the results (Table 1), the crystallite size seems to relate with dielectric
D

constant (ε), viscosity (η) and boiling point (Tb) of the alcohol solvents. The solvents
E

with a lower dielectric constant resulted in a smaller crystallite size than those with a
PT

higher dielectric constant [34]. The particle size decreases as the number of carbon
in the alcohol increases, leading to smaller crystallite size. Moreover, the different
CE

alcohol solvents can play the role in the crystallite size of products which were found
to relate with their boiling point and viscosity. The crystallite size of TiO2 particles
AC

increases as the decreasing boiling point and viscosity of alcohol solvents [34].
The agglomeration of TiO2 nanoparticles in different alcohol solvents was
explained. Farrokhi-rad and Ghorbani [42] had measured the zeta potential of TiO2
nanoparticles in different alcohols (methanol, ethanol, isopropanol and butanol) and
found that the absolute value of zeta potential decreases with increasing the
molecular size (carbon chain length) of alcohol. The zeta potential demonstrated the
variation of the dispersion stability of TiO2 particles in alcohol solvents. The higher
zeta potentials presented an increasing of electrostatic repulsion between the two
neighboring primary particles, leading to their separation and reduction the frequency
 ACCEPTED MANUSCRIPT
6

of successful collision of particles participating in Brownian motion [42, 43]. Thus, the
particles were reduced in different sizes. The particles in the suspension undergo
randomized Brownian motion which is significant for particle size of < 1 µm. The
diffusion coefficient of colloidal particles (D) in a suspension was determined by
fundamental Einstein’s equation [42]
(2)

, where k is Boltzmann’s constant, T is absolute temperature, d is particle diameter

PT
and η is the viscosity of solvent. For the smaller particles and lower viscosities,
colloidal particles have larger diffusion coefficient. Thus, TiO2 nanoparticles can

RI
diffuse and collide with each other more frequently in the suspension in sequence:
methanol > ethanol > isopropanol > 1-butanol, leading to the agglomerate growth

SC
rate increases. Dogon and Golombok [44] had concluded that smaller particles
agglomerated faster than larger particles. Due to the SEM images shown in Fig. 1,
NU
TiO2 nanoparticles in methanol produced larger particle size than those in ethanol
and 1-butanol, as the results summarized in Table 1.
MA

Fig. 5a shows the Raman spectra of TiO2 films prepared in ethanol, methanol,
1-butanol and isopropanol solvents. The tetragonal anatase has I41/amd space
group and contains six Raman active modes (A1g + 2B1g + 3Eg) [2]. All of the
D

samples have similar peaks appearing at 143, 394, 513 and 635 cm–1,
E

corresponding to the Eg, B1g, A1g and Eg modes of anatase phase, respectively. They
PT

have been known that Eg and B1g peaks are mainly caused by symmetric stretching
vibration and bending vibration of O–Ti–O, while A1g peak is caused by anti-
CE

symmetric bending vibration of O–Ti–O [39, 45]. Meanwhile, Raman peaks of the
samples shows different intensities controlled by their crystallite size and crystalline
AC

degree [46]. The improvement of crystallinity of anatase phase prepared in methanol

solvent can be explained by the decrease in boiling point and viscosity of alcohol
with decreasing in the length of carbon chains.
The FTIR spectra disclose chemical bonding information of the TiO 2 films
prepared in different solvents as the results shown in Fig. 5b. The absorption broad
band at 3421 cm–1 assigned to the hydroxyl groups (O–H) [45, 47, 48] and that at
1637 cm–1 ascribed to the H–O–H bending vibration, indicating that TiO2 contains
physically absorbed water on the surface [42, 49]. The band at 1384 cm–1 can be
assigned to C–OH or C–H stretching vibration. Meanwhile, the FTIR spectra of TiO2
 ACCEPTED MANUSCRIPT
7

films show intense broad band in the vicinity of 400–800 cm−1, corresponding to Ti–
O–Ti asymmetric stretching as expected for TiO2 [47, 48]. They should be noted that
the broad band at 3421 cm−1 and narrow band at 1637 cm−1 gradually changed with
different alcohol solvents and crystalline degree of TiO2 particles. In conclusion, the
crystallization process was influenced by the surface hydroxyl groups interacted with
the alcohol solvents [49]. Raman and FTIR spectra indicated the typical anatase
TiO2 phase and these results were also in accordance with the above XRD results.

PT
UV-visible spectroscopy and the plots of versus photon energy ( ) of
TiO2 films prepared in different alcohol solvents are shown in Fig. 6. The

RI
transmittance of the TiO2 films changed with the alcohol solvents. When photon
energy is greater than energy gap, the absorption is linearly increased with

SC
increasing of photon energy. Inclination of the linear portion was controlled by
charged diffusion from conduction band to valence band. The band gap (Eg) of a
NU
semiconductor can be calculated by the relationship between the absorption
coefficient and the incident photon energy by the following equation
(3)
MA

, where A is a constant, is the frequency of the incident photon and h is the

Planck’s constant, n = 2 for indirect transition [2, 41]. The absorption coefficient (α)
D

was calculated by , where T and d are the transmittance and the film
E

thickness, respectively [2]. For the plot of vs ( ), the indirect energy gap of
PT

TiO2 films was obtained by extrapolating the linear portion of the plot to zero
absorbance. They were found to be 3.30, 3.25, 3.20 and 3.00 eV for ethanol,
CE

1-butanol, methanol and isopropanol, respectively.

AC

4. Conclusions
The influence of alcohol solvents (methanol, ethanol, isopropanol and
1-butanol) on TiO2 films prepared by sol–gel method is reported. The study showed
that all of the fabricated samples had the crystalline structure of anatase phase. The
different alcohol solvents have the influence on the morphology, crystalline degree
and energy band gap. In additional, the crystallite size and agglomeration of TiO2
particles were found to be controlled by different alcohol solvents related to the
number of carbon in alcohol, boiling point, dielectric constant and viscosity. In this
 ACCEPTED MANUSCRIPT
8

research, the energy band gaps of the as-prepared TiO2 were determined to be
3.00−3.30 eV.

Acknowledgment: We wish to thank the Thailand Research Fund and the

Thailand’s Office of the Higher Education Commission for providing financial support
through the contact MRG6080011.

References

PT
[1] D. A. H. Hanao, C. C. Sorrell, J. Mater. Sci. 46 (2011) 855–874.
[2] W. promnopas, S. promnopas, T. Phonkhokkong, T. Thongtem, D. Boonyawan,

RI
L. Yu, O. Wiranwetchayan, A. Phuruangrat, S. Thongtem, Surf. Coatings

SC
Technol. 306 (2016) 69–74.
[3] A. Qu, H. Xie, X. Xu, Y. Zhang, S. Wen, Y. Cui, Appl. Surf. Sci. 375 (2016) 230–
NU
241.
[4] X. H. Lin, Y. Wu, J. Xiang, D. He, S. Fong, Y. Li, Appl. Catal. B 199 (2016) 64–
74.
MA

[5] S. Kathirvel, C. Su, Y. J. Shiao, Y.-F. Lin, B. R. Chen, Sol. Energy 132 (2016)
310–320.
D

[6] J. Liu, J. Luo, W.-G. Yang, Y.-L. Wang, L.-Y. Zhu, Y.-Y. Xu, Y. Tang, Y.-J. Hu,
C. Wang, Y.-G. Chen, W. Shi, J. Mater. Sci. Technol. 31 (2015) 106–109.
E

[7] S. Nagai, G. Hirano, T. Bessho, K. Satoria, Vib. Spectrosc. 72 (2014) 66–71.

PT

[8] S. J. Kwon, H. B. Im, J. E. Nam, J. K. Kang, T. S. Hwang, K. B. Yid, Appl. Surf.

Sci. 320 (2014) 487–493.
CE

[9] D. Mardare, N. Cornei, C. Mita, D. Florea, A. Stancu, V. Tiron, A. Manole, C.

Adomnitei, Ceram. Int. 42 (2016) 7353–7359.
AC

[10] J. Wu, C. Zhang, Q. Li, L. Wu, D. Jiang, J. Xia, Solid State Ionics 292 (2016)
32–37.
[11] O. Alev, E. Sennik, N. Kılınç, Z. Z. Öztürka, Procedia Eng. 120 (2015) 1162–
1165.
[12] R. Gao, Z. Jiao, Y. Wang, L. Xu, S. Xia, H. Zhang, Chem. Eng. J. 304 (2016)
156–164.
[13] L. Yang, H. Z. Li, J. Liu, Y. Lu, S. Li, J. Min, N. Yan, Z. Men, M. Lei, J. Alloys
Compd. 689 (2016) 812–819.
 ACCEPTED MANUSCRIPT
9

[14] Y. Zhao, W. Zhu, G. Z. Chen, E. J. Cairns, J. Power Sources 327 (2016) 447–
456.
[15] Z. Liu, X. Zhang, T. Murakami, A. Fujishima, Sol. Energy Mater. Sol. Cells 92
(2008) 1434–1438.
[16] G. Wang, W. Feng, X. Zeng, Z. Wang, C. Feng, D. T. McCarthy, A. Deletic, X.
Zhang, Water Res. 94 (2016) 363–370.
[17] S. Sun, P. Gao, Y. Yang, P. Yang, Y. Chen, Y. Wang, Appl. Mater. Interfaces 8
(2016) 18126–18131.

PT
[18] B. Wu, D. Liu, S. Mubeen, T. T. Chuong, M. Moskovits, G. D. Stucky, J. Am.
Chem. Soc. 138 (2016) 1114–1117.

RI
[19] C. Guillѐn, J. Montero , J. Herrero, J. Mater. Sci. 49 (2014) 5035–5042.

SC
[20] B. Houng, Y. H. Shih, S. H. Lu, W. C. Chien, J. Electroceram. 36 (2016) 87–93.
[21] D. Guo, A. Ito, T. Goto, R. Tu, C. Wang, Q. Shen, L. Zhang, J. Adv. Ceram. 2(2)
NU
(2013) 162–166.
[22] C. Edusi, G. Sankar, I. P. Parkin, Chem. Vap. Deposition 18 (2012) 126–132.
[23] R. A. Antunes , M. C. L. de Oliveira , M. F. Pillis, Int. J. Electrochem. Sci. 8
MA

(2013) 1487–1500.
[24] S. Dhanapandian, A. Arunachalam, C. Manoharan, J. Sol-Gel Sci. Technol. 77
D

(2016) 119–135.
[25] J.-J. Park, D.-Y. Kim, S. S. Latthe, J.-G. Lee, M. T. Swihart, S. S. Yoon, Appl.
E

Mater. Interfaces 5 (2013) 6155−6160.

PT

[26] A. Ishii, Y. Nakamura, I. Oikawa, A. Kamegawa, H. Takamura, Appl. Surf. Sci.

347 (2015) 528–534.
CE

[27] O. Wiranwetchayan, Q. Zhang, X. Zhou, Z. Liang, P. Singjai, G. Z. Cao,

Chalcogen. Lett. 9 (2012) 157–163.
AC

[28] M. A. Behnajady, H. Eskandarloo, Res. Chem. Intermed. 41 (2015) 2001–2017.

[29] R.S. Sabry, Y. K. Al-Haidarie, M. A. Kudhier, J. Sol-Gel Sci. Technol. 78 (2016)
299–306.
[30] S. Šegota, L. Ćurkovic, D. Ljubas, V. Svetličić, I. F. Houra, N. Tomašić, Ceram.
Int. 37 (2011) 1153–1160.
[31] S. El-Sherbiny, F. Morsy, M. Samir, O. A. Fouad, Appl. Nanosci. 4 (2014) 305–
313.
[32] J. Yue, Z. Chen, Y. E, L. Chen, J. Zhang, Y. Song, Y. Zhai, Nanoscale Res. Lett.
9 (2014) 1–6.
 ACCEPTED MANUSCRIPT
10

[33] W. Thongsuwan, T. Kumpika, P. Singjai, Curr. Appl. Phys. 8 (2008) 563–568.

[34] Y.-C. Wu, Y.-C. Tai, J. Nanopart. Res. 15 (2013) 1–11.
[35] B. Duymaz, Z. V. Yigit, M. G. Seker and F. Dündar, Acta Phys. Pol. A 129
(2016) 872–874.
[36] S. Segota, L. Curkovic, D. Ljubas, V. Svetlicic, I. F. Houra, N. Tomasic, Ceram.
Int. 37 (2011) 1153–1160.
[37] S. Collette, J. Hubert, A. Batan, K. Baert, M. Raes, I. Vandendael, A. Daniel, C.
Archambeau, H. Terryn, F. Reniers, Surf. Coat. Technol. 289 (2016) 172–178.

PT
[38] Powder Diffract. File, JCPDS-ICDD, 12 Campus Boulevard, Newtown Square,
PA 19073-3273, U.S.A., (2001).

RI
[39] Y. Cao, Q. Li, C. Li, J. Li, J. Yang, Appl. Catal. B 198 (2016) 378–388.

SC
[40] M. Stefan, O. Pana, C. Leostean, C. Bele, D. Silipas, M. Senila, E. Gautron,
J. Appl. Phys. 116 (2014) 1–13.
NU
[41] O. Wiranwetchayan, W. Promnopas, K. Hongsith, S. Choopun, P. Singjai,
S. Thongtem, Res. Chem. Intermed. 42 (2016) 3655–3672.
[42] M. Farrokhi-rad, M. Ghorbani, Ceram. Inter. 38 (2012) 3893–3900.
MA

[43] G. Borsoi, B. Lubelli, R. van Hees, R. Veiga, A. Santos Silvad, L. Collae,

L. Fedele, P. Tomasin, Colloids Surf. A: Physicochem. Eng. Aspects 497 (2016)
D

171–181.
[44] D. Dogon, M. Golombok, J. Petrol. Explor. Prod. Technol. 5 (2015) 91–98.
E

[45] F. Tian, Y. Zhang, J. Zhang, C. Pan, J. Phys. Chem. C 116 (2012) 7515−7519.
PT

[46] M. K. Ahmad, S. M. Mokhtar, C. F. Soon, N. Nafarizal, A. B. Suriani,

A. Mohamed, M. H. Mamat, M. F. Malek, M. Shimomura, K. Murakami, J. Mater.
CE

Sci.: Mater. Electron. 27(2016) 7920–7926.

[47] S. H. Othman, S. Abdul Rashid, T. I. Mohd Ghazi, N. Abdullah, J. Nanomater.
AC

2012 (2012), 1–10.

[48] A. Qu, H. Xie, X. Xu. Y. Zhang, S. Wen. Y. Cui, Appl. Surf. Sci. 375 (2016)
230–241.
[49] B. M. Rao, S.C. Roy, J. Phys. Chem. C 118(2014) 1198−1205.
 ACCEPTED MANUSCRIPT
11

Figure captions

Fig. 1 FE-SEM images of TiO2 films prepared by sol-gel method in different alcohol
solvents: (a) ethanol, (b) methanol, (c) 1-butanol and (d) isopropanol.

Fig. 2 TEM images and SAED patterns of TiO2 prepared in different alcohol solvents:
(a) ethanol, (b) methanol, (c) 1-butanol and (d) isopropanol.

PT
Fig. 3 HR-TEM images of TiO2 prepared in different alcohol solvents: (a) ethanol, (b)
methanol, (c) 1-butanol and (d) isopropanol.

RI
SC
Fig. 4 XRD patterns of TiO2 films prepared in different alcohol solvents comparing
with the JCPDS database.
NU
Fig. 5 (a) Raman and (b) FTIR spectra of TiO2 films prepared in different alcohol
solvents.
MA

Fig. 6 Transmittance and the plots of versus photon energy ( ) of TiO2

D

films prepared in different alcohol solvents.

E
PT
CE
AC
 ACCEPTED MANUSCRIPT
12

(a) (b)

PT
200 nm 200 nm

RI
(c) (d)

SC
NU
MA

200 nm 200 nm
D

Fig. 1
E
PT
CE
AC
 ACCEPTED MANUSCRIPT
13

(a) (b)

PT
RI
(c) (d)

SC
NU
MA
DE

Fig. 2
PT
CE
AC
 ACCEPTED MANUSCRIPT
14

(a) (b)

PT
RI
(c) (d)

SC
NU
MA
D

Fig. 3
E
PT
(101)

Isopropanol
Ethanol
Methanol
CE

Butanol
(200)
(004)

(211)
(105)
Intensity (a.u.)

(204)

(116)
(220 )

(215)
AC

Isopropanol

Ethanol

Methanol

Butanol
JCPDS file no. : 21-1272

20 30 40 50 60 70 80
2 (degree)

Fig. 4
 ACCEPTED MANUSCRIPT
15

(a)

-1
Isopropanol Methanol

143 cm
Ethanol 1- Butanol

-1
-1

635 cm
-1

513 cm
Intensity (a.u.)

394 cm
Isopropanol

PT
Ethanol

Methanol

RI
1- Butanol

SC
100 200 300 400 500 600 700 800
Raman shift (cm )
-1
NU
(b)
MA

Iopropaanol
Ethanol
1384

Methanol
1637

1-Butanol
Transmittance (a.u.)

E D 3421

475

Iopropanol
PT

Ethanol

Methanol
CE

1-Butanol
AC

4000 3500 3000 2500 2000 1500 1000 500

-1
Wavenumber (cm )

Fig. 5
 ACCEPTED MANUSCRIPT
16

100
90 Transmittance(%)
80 Ethanol
70
Methanol
(αhν)1/2 (a.u.) 60
Isopropanol
50
40 1-Butanol
30
20
10

PT
0
300 350 400 450 500 550 600 650 700 750 800
1-Butanol
Methanol
Ethanol

RI
Isoprppanol

1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0

SC
hν (eV)

Fig. 6
NU
MA
E D
PT
CE
AC
 ACCEPTED MANUSCRIPT
17

Table 1. The properties of alcohol solvents and average size of TiO2 nanopaticles.

Crystallite Particle
Boiling Viscosity
Alcohol Chemical Dielectric size size
points at 20oC
solvents formulae constants (Scherrer) (SEM)
(°C) (mPa.s)
(nm) (nm)
ethanol C2H6O 24.6 78.24 1.20 11.9 83
methanol CH3OH 32.6 64.7 0.59 12.2 85

PT
1-butanol C4H10O 17.5 117.7 2.95 9.3 70
isopropanol C3H8O 19.9 82.6 2.38 10.1 -

RI
SC
NU
Table 2. The d-spacing values and Miller indices of anatase TiO2 prepared in
different alcohol solvents as compared with those of the JCPDS database no. 21-
MA

1272 [38].
d-spacing values (nm)
JCPDS Miller indices
D

Ethanol Methanol Butanol Isopropanol

database (hkl)
E

0.352 0.347 0.351 0.352 0.355 (101)

PT

0.238 0.231 0.231 0.239 0.231 (004)

0.189 0.190 0.184 0.187 0.188 (200)
CE

0.167 0.166 0.163 0.166 0.166 (211)

0.148 0.147 0.144 0.146 0.145 (204)
AC
 ACCEPTED MANUSCRIPT
18

Highlights

 Anatase films were successfully prepared in different alcohol solvents.

 The solvents can play role in crystallite size, crystalline degree and
energy gap.

PT
 The promising material for a number of applications.

RI
SC
NU
MA
E D
PT
CE
AC