2019

PROJECT REPORT

A COMPARATIVE STUDY ON PHASE

IDENTIFICATION OF MICRON LEVEL (DIA:
15 µm, 50 µm AND 100 µm; THICKNESS:
10 nm, 50 nm AND 100 nm) METAL
OXIDE SAMPLE USING MICRO-RAMAN,
MICRO-XRD, SA-XPS

NE201 MICRO AND NANO CHARACTERIZATION METHODS

PROJECT 8 – GROUP 1
ARNAB KAR, GOPINATH N.K, SOUGATA MANDAL, SUBRATA DAS, DHANPAL BAIRWA

IISc | Bangalore Submitted on 29-Apr-2019

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 Table of Contents
Abstract .......................................................................................................................................... 3

1. Introduction ........................................................................................................................... 3

2. Experimental Methodology .................................................................................................. 4

2.1 Sample Preparation .......................................................................................................... 4

2.2 Micro-Raman ................................................................................................................... 5

2.3 X-ray Diffraction .............................................................................................................. 5

2.4 Selected area X-ray Photoelectron Spectroscopy............................................................. 5

3. Results and Discussion .......................................................................................................... 6

3.1 Morphology of the micro-dots ......................................................................................... 6

3.2 Phase identification by Micro-Raman .............................................................................. 7

3.3 Phase identification by Glancing angle XRD ................................................................ 10

3.4 Phase identification by SA-XPS .................................................................................... 11

3.5 Comparison of phase characterization techniques ......................................................... 13

4. Conclusions........................................................................................................................... 14

Acknowledgement ....................................................................................................................... 15

References .................................................................................................................................... 16

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 A COMPARATIVE STUDY ON THE PHASE
IDENTIFICATION OF MICRON LEVEL (DIA: 15 µm, 50 µm
AND 100 µm; THICKNESS: 10 nm, 50 nm AND 100 nm)
METAL OXIDE SAMPLE USING MICRO-RAMAN, MICRO-
XRD, SA-XPS
Arnab Kar1, Gopinath N.K2, Sougata Mandal1, Subrata Das1, Dhanpal Bairwa1
1
Department of Physics, Indian Institute of Science, Bangalore 560012
2
Department of Aerospace Engineering, Indian Institute of Science, Bangalore 560012

Abstract
This report discusses the phase identification of micron level titanium oxide on silicon substrate at
varying thickness and diameter using micro-Raman, X-ray diffraction and selected area X-ray
photoelectron spectroscopy. Micro-dots of the titanium oxide having diameter 15 µm, 50 µm and
100 µm, with thickness 10 nm, 50 nm and 100 nm have been prepared using optical lithography
technique and annealed to obtain crystalline phase. Raman equipped with confocal microscope
setup provide lateral resolution of 1µm, which is able to identify the micron level titania for all the
combinations of thickness and diameters. In case of X-ray diffraction, under glancing angle mode,
none of the individual micro-dots could be identified, due to the low interaction volume and also
due to unavailability of the micro-XRD setup. Selected area-XPS can detect the 15 µm micro-dot
of TiO2. However, at thickness of 50 nm and 10 nm, sample preparation difficulty and/or lack of
detection is observed. Taken together, micro-Raman identifies the micron-level metal oxide phases
better than other techniques and can be used as a sensitive local probing technique.

1. Introduction
Metal oxides with wide band-gap and high dielectric constant, are being actively researched for
applications in electronic industry. Especially metal oxides, such as Al2O3, ZrO2, and TiO2, are
widely used in optical devices, chemical sensors, environmental remediation, etc.1,2 Particularly,
TiO2 finds application as photocatalyst for removing water pollutants, hydrogen generation from
water, as well as in solar cells.3,4,5However, the phase composition of TiO2 is critical parameter to
be known, as it controls the electronic properties and catalytic activity.2

In general, TiO2 exists in five crystalline phases viz., tetragonal anatase, tetragonal rutile,
orthorhombic brookite, orthorhombic TiO2-II and monoclinic baddeleyite, in addition to the
amorphous phase.6 Rutile and anatase are the common polymorphs of titania, which has the same
point group symmetry 4/mmm, despite having different structures.7 In Rutile, the structure is based
on octahedrons of titanium oxide which share two edges of the octahedron with other octahedrons
and form chains, showing four-fold symmetry. In anatase, the octahedrons share four edges and

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hence the four-fold axis. Thus, there should be suitable characterization technique to identify the
phases, even if the presence is in micron level, in order to enable process control for targeted
formation of particular phase.

Hugman et al. (2003) studied 70 nm thick titania coating on silicon for solar applications using
micro-Raman and glancing angle XRD at different annealing temperatures and reported phase
evolution.8 Similarly, Wang et al. (2014) prepared multi-layer oxygen sensor with 54 nm titania
coating using chemical vapor deposition and analyzed the phase of TiO2 using XRD and found to
be anatase.9Leprince-Wang (2002), investigated very thin TiO2films, with thickness as low as 0.17
nm, prepared using electron beam evaporation on Si wafers, and detected the chemical
composition and stoichiometry of phases using XPS.10

With this brief background, this project aims to find the limiting capacity of commonly used phase
identification techniques, though identification of micron level impurity (impurity diameter: 15
µm, 50 µm and 100 µm; impurity thickness: 10 nm, 50 nm and 100 nm) in samples. Specifically, in
this work we study the phase identification of TiO2 micro-dots on Si(100) substrate using three
characterization techniques namely micro-Raman, X-ray diffraction and selected area X-ray
photoelectron spectroscopy. This report is organized such that section 2 provides details on the
experimental methodology, including sample preparation and characterization methods used.
Section 3 details on the phase identification results obtained from the characterization methods
and section 4 provides the conclusion and future scope of work.

2. Experimental Methodology
2.1 Sample Preparation
Optical lithography and sputtering technique is used for preparing the TiO2 micro-dots on Si(100)
substrate. Substrate of size ~25 mm x ~25 mm is initially cleaned by following the standard RCA
1 and 2 procedure, with HF dip to remove native oxide. Lithography using Heilderberg Mask
Writer with AZ5214Epositive photoresist is performed to obtain the pattern with 15 µm, 50 µm
and 100 µm dots, as shown in Fig. 1. Following this, sputter coating of TiO2 is done with 100 W
power in room temperature with base pressure of 10-6 torr. The approximate deposition rate is 3.3
nm/min and the thickness tolerance is ±5%. Finally, acetone IPA etching is done for 30 minutes
to lift off the mask from the substrate. After the fabrication of the samples, annealing is conducted
using Lindberg Furnace at temperature of 4500C and holding time of 1 hour in ambient atmosphere
to ensure crystallinity.

Two batches of samples have been prepared for all the combinations of diameters and thicknesses,
with one containing sequence of micro-dots (Fig. 1a) and other with individual micro-dots (Fig.
1b). While the sequence of micro-dots can provide the lateral resolution information of the
characterization equipment, the individual micro-dots samples aid in detecting the micron-level

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impurity, which is the primary aim of this project. The individual micro-dots samples are diced
using a Silicon dicer such that single dot is present at the center of the sample.

(a) (b)
Fig. 1 Schematic of the design used in the sample fabrication using lithography technique. Design
with (a) sequence of micro-dots and (b) individual micro-dots is shown.

2.2 Micro-Raman
The vibrational modes of the TiO2 micro-dots are studied by recording the Raman spectra using
HORIBA Jobin Yvon Labram HR 800 equipped with CCD detector and 532 nm DPSS Laser as
excitation source. Confocal microscope attachment with 100X magnification and 100 µm pinhole
aperture enabled the lateral resolution of 1 µm and the laser full power on the sample at this
magnification was around 12mW, with neutral density filter. Wavenumber sweep are performed
in two ranges i.e., 50 to 500 cm-1 and 542 to 900 cm-1, in order to avoid the significant substrate
peak. The scan duration for 1 set of measurement is around 1 minute.

2.3 X-ray Diffraction

X-ray diffraction (XRD) technique is employed to identify the phase assemblage of micro-dots.
XRD analyses are conducted in Rigaku XRD machine, with CuKα radiation (λ=0.15406 nm),
under the constant voltage and current of 40 kV and 30 mA, respectively. Glancing angle XRD
has been performed to enhance the interaction volume with the sample and thus Normal XRD was
not done as the X-ray penetration could be significant. Here, glancing angle XRD with incidence
angle at 0.5o and 1o is used with scan rate of 1o/min and 0.01 as step size. Trials with 2D detector
could not detect the peaks as it is functional only in Normal XRD, and hence 0D detector with
glancing mode is used to improve the signal quality. Due to technical difficulties, micro-XRD
could not be performed, though the slit with 0.002 mm size is available. All the measurements are
performed with the slit size of 2 mm, as the use of 0.5 mm slit results in poor signal to noise ratio.
The experimental XRD patterns are compared with ICSD database to identify the phases.

2.4 Selected area X-ray Photoelectron Spectroscopy

Selected area X-ray Photoelectron Spectroscopy (SA-XPS) has been conducted using a high-
resolution spectrometer (Axis Ultra DLD, Kratos Analytical), equipped with monochromatic AlKα
X-ray radiation source (hν=1486.6 eV) under vacuum of 3 × 10−9 torr. Survey scans in the range
of 0-1400 eV with pass energy of 160 eV and step size of 1 eV and narrow fine scans for elemental

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spectra with pass energy of 20 eV and step size of 0.1 eV is performed. Dwell time and sweeps
are 300 s and 2 for wide scan and 700 s and 7 high resolution scans. Aperture control for SA-XPS
mode are available in the range of 15 µm, 27 µm, 55 µm, 110 µm and 300 µm. To improve the
signal to noise ratio for the micro-dots, aperture control with scan area of 300 µm x 700 µm, is
used which is smaller than the generally used 2 mm x 2 mm. C1s peak at 284.5 eV from
adventitious carbon is considered as reference for calibration. The background signals are removed
using Shirley method and the photoelectron peaks are deconvoluted using Gaussian/Lorentzian
peak fitting, such that residuals are in the range of 0.95-0.99. The post-processing is performed
using CASA-XPS software package.

Also, optical profilometer (Dektak-XT) is used to inspect the micro-dots and ellipsometer (M-
2000 Woollam) is used to verify the thickness and refractive index of the micro-dots. Additionally,
Scanning Electron Microscopy (SEM) equipped with Energy Dispersive Spectrometry (EDS)
(Ultra 55, Carl Zeiss, Germany), operated at accelerating voltage up to 10 keV, is used to check
the diameter of the fabricated micro-dots, and also obtain the elemental mapping.

3. Results and Discussion

3.1 Morphology of the micro-dots
Dimensions of the fabricated samples are verified by using optical profiler, SEM and ellipsometer.
Table 1 lists the thickness and refractive index from ellipsometer and diameter from SEM. The
mean square error for all the parameters is about 10%. This ensures that the desired requirements
for the fabrication are met. Representative secondary electron micrographs for three diameters
(thickness of 100 nm) are shown in Fig. 2. The elemental mapping from EDS, is given in Fig. 3,
which shows the presence of Ti in the micro-dot region, along with O. Area EDS within the micro-
dot is also shown in Fig. 3 which reveal the composition to be TixOy, with y/x ~ 2.5.

Table 1: Dimensional verification of the fabricated TiO2 micro-dots.

Samples Thickness (nm) Refractive index @ 632 nm Diameter (µm)

1 10.7 2.26 15.1
2 51.1 2.38 50.3
3 100.4 2.41 100.2

Fig. 2: Micrographs of the TiO2 micro-dots with 100 nm thickness, showing the diameters for the
three case of: (a) 15 µm; (b) 50 µm; (c) 100 µm.

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Fig. 3: EDS mapping of the 100 nm thick and 100 µm dia TiO2 micro-dot showing (a) SE image;
(b) Ti map; (c) O map; (d) Si map; (e) EDS spectra, along with the composition table.

3.2 Phase identification by Micro-Raman

Figure 4 shows the micro-Raman spectra of Si substrate and TiO2/Si sample of 100 nm thickness
annealed at 4500C. The discontinuous spectrum plotted from 50 cm-1 to 900 cm-1, primarily arises
from the wave number sweep, to avoid the strong characteristic peak of silicon substrate at 520.5
cm-1. This was done to avoid the intensity scaling of the micron-level TiO2, which could affect the
detectability. The spectra also shows other Si peaks located at 301.4 cm-1, 435.4 cm-1, 617.5 cm-1
and 671.6 cm-1.8 For the TiO2/Si samples, an additional strong peak at 142.6 cm-1 along with peaks
at 197.7cm-1,391.4 cm-1 and 631.8 cm-1, confirm the presence of TiO2 in the substrate. These peaks
correspond to anatase phase of TiO2, which confirms the crystallinity achieved via annealing up
to 4500C. Moreover, there is no presence of rutile phase, which is plausible from the moderate
temperature heat treatment. Comparing with the reported data in literatures,8,11Raman modes
observed in the current samples show only minor deviation in the Raman shift. This is likely since
there could be slight stoichiometry deviation of different morphologies from different synthesis
methods. The variation from stoichiometry can be qualitatively seen from the EDS analysis, which
shows TixOy, with y/x ~2.5. The processing conditions have been reported to influence Raman
peak positions as well as the peak broadening (FWHM) effects.12

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Fig. 4: Micro-Raman spectra of the substrate and the micro-dot of 100 nm thickness and 10 μm dia.

The effect of diameter variation (100 μm, 50 μm, 15 μm) for constant thickness is studied and the
Raman spectra are shown in Fig. 5. Figure 5a, 5b and 5c correspond to thickness of 100 nm, 50
nm, and 10 nm, respectively. It is noticed that, the intensity decreases with decreasing diameter,
which seems to follow linear trend. This could be probably to reasoned to the reduction in the
amount of TiO2, with decrease in diameter, which results in low photon-matter interaction.
Extending the same argument to the case of the 10 nm samples, the intensity of the strong peaks
at 142 cm-1 is significantly low as compared to 100 nm and 50 nm, which could be reasoned to the
same effect of low photon interaction with TiO2.

(a) (b)

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 (c)

Fig. 5: Effect of diameter variation (100 μm, 50 μm, 15 μm) for (a)100 nm, (b) 50 nm, and (c) 10
nm thickness.

The effect of thickness variations (100 nm, 50 nm, 10 nm) for same diameter is represented in Fig.
6, wherein for the case of 100 μm, 50 μm and 15 μm, are respectively shown in Fig. 6a, 6b, and
6c. With increasing thickness, the peaks at 197 cm-1, 391 cm-1 and 631 cm-1 shows decrease in
intensity. For the 50nm samples, 391 cm-1 peak is not evident and for 10 nm samples, the peaks at
197 cm-1 and 631 cm-1 also are not present. This is because of less interaction as mentioned
previously. Also, the shift in the strong peak at 142 cm-1 to the lower wavenumber (higher
frequency) is noted. For bulk anatase crystalline phase this peak generally comes at 144.3 cm -1.13
In the present samples, these shifts are due to inhomogenous strain field induced during the growth
caused by lattice mismatch between Si substrate and antase phase, which should decrease with
increasing thickness.14 To investigate this, we have plotted the variation in the Raman shift for
varying thickness and diameter, which shown in Fig. 6d. This figure shows that the aforementioned
statement is indeed the case. It is also noted from Fig. 6a,6b,6c that the intensity for 50 nm is more
than others. This may be due to the increased background intensity in 50 nm samples as we can
clearly see in the figures near the starting point (70 cm-1).

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 (a) (b)

(c) (d)

Fig. 6: Effect of thickness variation (100 nm, 50 nm, 10 nm) for (a)100 μm, (b) 50 μm, and (c) 15
μm thickness; (d) Variation of the Raman shift with the thickness and diameter.

3.3 Phase identification by Glancing angle XRD

Based on Raman studies the phase that attained by the sample is confirmed to be anatase. Further,
XRD is conducted to confirm the TiO2 detectability and its phase. It is to be mentioned that XRD
measurement is done on the chain of micro-dots (Fig. 1a) of dimension 100nm thickness and 100
μm diameter. From the ICSD file it is known that for the anatase phase of TiO2 a strong peak
comes at about 2𝜃 = 260 and a small peak at 2𝜃 = 390 .12 In the present case, XRD shows peak
at 2𝜃 = 25.30 , which is assigned to TiO2. However, other peaks at higher 2𝜃 couldn’t be obtained
due to high background, resulting in poor signal to noise ratio, even with 0D detector. As per the

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project requirements, the measurements are also tried with the single dot (Fig. 1b) specimens,
using 0D and 2D detectors, but no peaks could be detected. This is reasoned to the low interaction
with TiO2, even in glancing angle mode of XRD. Thus, the unavailable of micro-XRD has resulted
in the inability to detect the TiO2 micro-dots. However, multiple trials have been tried changing
the parameters (detector type, grazing angle, scan rate etc.) and it can be claimed that glancing
angle XRD provides some inputs on phase identification of micron level impurity, but unable to
provide the required resolution as per the project requirement.

Fig. 7: X-ray diffractogram of the TiO2 sequence of micro-dots for the case of 100 nm thickness
and 100 μm diameter, showing the characteristic anatase peak.

3.4 Phase identification by SA-XPS

Selected area XPS study is carried out for the six combinations of TiO2 micro-dots (Fig. 1(b)),
which corresponds to thickness of 100 nm, 50 nm and diameter of 100 μm, 50 μm, 15 μm. For the
case of 10 nm thick samples, the difficulty in locating the dots under optical microscope is present.
Thus, the samples couldn’t be cut to individual pieces and also mark the location of the micro-dots
for SA-XPS. The survey spectra for 100 nm and 100 μm TiO2 is given in Fig. 8. The wide scan
shows the presence of characteristic peaks from Si2p, Si2s, C1s and, but without Ti2p. The absence
of clearly recognizable Ti peak in the wide scan is possible due to the high pass energy and larger
step size used. However, in the narrow scans, signals from Ti core level spectra could be obtained.
The high-resolution photoelectron spectra for different combinations of thickness and diameters
for Ti2p and O1s are shown in Fig. 9, and the deconvoluted values are given in the Table 2.

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The Ti2p spectra reveal the presence of spin-orbit coupled doublets 2p1/2 and 2p3/2, located at 459.1
eV and 464.7 eV, with intensity ratio of 1:2. This corresponds to bonding of Ti-O in the TiO2, with
Ti in +4 oxidation state.15 Similarly, the deconvoluted O1s spectra shows two peaks with one
centered at 532.5 eV and other at 531.1 eV. These are ascribed to O-Ti bonds in TiO2 and
adventitious oxygen from environment, respectively. From Fig. 9 it is noted that the intensity of
the Ti2p peaks increases with increase in the micro-dot size which is due to increase in the amount
of TiO2 compositions in the sample.16 As mentioned earlier, the other combinations which are not
shown in Fig. 9 could not be performed due to difficulty in sample preparation.

Table 2: Binding energy of different chemical bonds for varying thickness and diameter of TiO2.

Sample (Ti-O) (Ti-O) (O-Ti) (O-C) Intensity ratio

Specification Ti2p1/2 Ti2p3/2 O1s O1s of Ti doublets
100nm_100μm 458.1 464.7 532.5 531.1 2

100nm_50μm 457.7 464.4 532.2 531.2 1.76

100nm_15μm 457.7 462.8 533.7 531.8 2

50nm_100μm 457.9 465.4 532.3 531.2 2

50nm_50μm Nil Nil 532.4 531.2 Nil

50nm_15μm Nil Nil 532.1 531.2 Nil

(a) (b)

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 (c) (d)

(e) (f)
Fig. 9: Core level high resolution XPS spectra of Ti2p (a-d) and O1s (e-f). The deconvoluted
spectra corresponds to (a) Ti2p (100 nm, 100 μm); (b) Ti2p (100 nm, 50 μm); (c) Ti2p (100 nm,
15 μm); (d) Ti2p (50 nm, 100 μm); (e) O1s (100 nm, 100 μm) and; (f) O1s (100 nm, 15 μm).

3.5 Comparison of phase characterization techniques

A qualitative comparison has been made to study the variation of intensity from the three
characterization techniques used for phase identification of TiO2 micro-dots on Si(100) substrate.
Table 3 lists such comparative results, which clearly shows that micro-Raman is able to detect the
micron-level TiO2 for all the combinations of thickness and diameter. In case of XRD, the sample
with chain of dots, could be detected using glancing mode XRD with 0D detector. However, single
micro-dot could not be detected for any of the samples, due to low interaction volume of the micro-
dots. SA-XPS is able to detect the TiO2 micro-dots in most of the cases, except for 10 nm thickness,
which is not due to the limitation of the equipment, rather than the sample preparation involving
locating the micro-dot and dicing. Comparing the intensity levels between the techniques, it can
be noted that micro-Raman and SA-XPS provides good intensity for 100 nm thick samples of

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varying diameters. For the 50 nm thick samples, micro-Raman results are better as compared to
SA-XPS, especially for 50 μm and 15 μm diameter. In case of 10 nm samples, micro-Raman is
able to identify the presence of TiO2, however the intensity levels are poor. For XPS, the issue
with sample preparation rendered the measurement impossible.

Table 3: Qualitative comparison between the intensity levels of different phase characterization
techniques used for detection of micron-level metal oxide.

Sample Specification Characterization Technique

Micro-Raman Glancing XRD SA-XPS
100nm_100μm Good ---- Good
100nm_50μm Good ---- Good
100nm_15μm Good ---- Good
50nm_100μm Good ---- Good
50nm_50μm Good ---- Poor
50nm_15μm Good ---- Poor
10nm_100μm Poor ---- ----
10nm_50μm Poor ---- ----
10nm_15μm Poor ---- ----
---- represents the intensity couldn’t be recorded due to sample preparation
difficulty and/or lack of detection

4. Conclusions
Phase identification of optical lithography fabricated and annealed micro-dots of titania with
diameter of 15 µm, 50 µm and 100 µm and thickness 10 nm, 50 nm and 100 nm has been carried
out using micro-Raman, XRD and selected area XPS. The salient outcomes are listed below:

 The dimensions of the micro-dots are verified using SEM and optical profiler (for diameter)
and ellipsometer (for thickness). EDS data indicates the presence of TiO2 within the micro-
dot region. These confirms that the prepared samples are as per the required specifications.

 Micro-Raman is able to identify the phases for all the combinations. This is ascertained to
the confocal microscope setup which can provide lateral resolution as low as 1 µm. The
micron-level impurity of TiO2 is detected and the phase is identified as anatase. However,
for the 10 nm combination samples the intensity of the prominent peak (142.6 cm-1) is very
poor due to less thickness of the sample.
 As micro-XRD setup is not functional, normal XRD under grazing incidence is done.
While for 100 nm thick samples, the peaks corresponding to anatase at 25.3o is recorded
for the chain of micro-dots. However, even with varying the parameters (detector type,

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 grazing angle, scan rate etc.), the equipment is unable to detect the single dots due to low
interaction volume and higher exposure dimension of the X-ray on the substrates.

 In case of SA-XPS, the high-resolution scans are able to detect TiO2 impurities with lateral
size as low as 15 μm. However, for thickness of 50 nm, only 100 μm sized impurity can be
detected. For 10 nm thickness, the sample preparation difficulties resulted in inability to
obtain the XPS data.

Conclusively, it can be stated that micro-Raman identifies all the combination of micron-level
metal oxide phases better than other techniques and can be used as a sensitive local probing
technique. SA-XPS is also found to be a competing technique, which can identify and resolve
impurities with size as low as 15 μm. In case of XRD, there is further scope of improvement
through incorporate the micro-XRD arrangement and variation of different processing parameters
for identification of micron-level impurity.

Acknowledgement
We express our sense of gratitude to all the instructors and MNCF facility technologists of NE-
201 Jan-Apr 2019 session for their valuable teaching and support to learn about different
characterisation methods. In particular, our sincere thanks to Dr. Arunbabu A. V for his overall
support to the project; Mr. Varadharaja Perumal for his enthusiastic inputs on sample fabrication
and XPS measurements; Mr. Swaran Saseendran for Raman measurements; Mr. Pradeep M L for
helping in XRD measurements. We are also thankful to NNFC staff. Dr. Savitha P for granting
permission for sample fabrication and annealing; Mr. Shreyas Bhat for his consistent efforts to get
our samples fabricated; Ms. Supriya and Ms. Smitha for helping with the annealing; and Ms.
Vanitha for FOM access and help.

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