Applied Surface Science 218 (2003) 97–105

Influence of annealing temperature on the properties

of titanium oxide thin film
Ya-Qi Hou*, Da-Ming Zhuang, Gong Zhang, Ming Zhao, Min-Sheng Wu
Department of Mechanical Engineering, Tsinghua University, Beijing 100084, PR China
Received 31 October 2002; received in revised form 31 October 2002; accepted 26 March 2003

Abstract

The influence of annealing temperature on the micro-structure, surface morphology and optical property of TiO2 thin films
prepared by mid-frequency ac magnetron sputtering technique has been studied. The micro-structure and surface morphology
were examined by X-ray diffractometer (XRD) and atomic force microscopy (AFM). The transmittance and reflectance spectra
of TiO2 thin films on fused silica substrate were measured by spectrophotometer. The reflective indices and extinction
coefficients of TiO2 films were calculated by envelope method and experimental expression, respectively. The results show that
the TiO2 thin film sputtered at room temperature is amorphous. After annealing under lower temperature (¼700 8C), anatase
phase appeared in TiO2 thin film. After annealing under higher temperature (¼900 8C), the structure of TiO2 thin film changed
into rutile completely; the TiO2 grains changed from column to nubbly. The refractive index of TiO2 thin film increases with
annealing temperature and the extinction coefficient decreases a little during the lower temperature anneal. The TiO2 thin film
annealed at 500 8C has the best optical property.
# 2003 Elsevier B.V. All rights reserved.

Keywords: Titanium oxide thin film; Mid-frequency ac magnetron sputtering; Annealing; Anatase; Optical property

1. Introduction due to their high reflective index and transparency

over a wide spectral range [2].
TiO2 thin films are extensively studied because of For these reasons, so much techniques were used to
their interesting chemical, electrical and optical prop- achieve TiO2 thin film [4–6]. In all of these, magnetron
erties [1,2]. TiO2 film in anatase phase could accom- sputtering is one of the most easily to industrialize,
plish the photocatalytic degradation of organic and to achieve the high quality thin film in large area
compounds under the radiation of UV. So, it has a substrates [3,4]. Recently, mid-frequency ac magne-
variety of application prospects in the field of envir- tron sputtering using pure titanium target was studied
onmental protection [3,4]. TiO2 thin film with rutile widely [7,8]. In our laboratory, high quality TiO2 film
structure is known as a good blood compatibility has been prepared by mid-frequency ac magnetron
material and can be used as artificial heart valves sputtering successfully [9].
[5]. In addition, TiO2 films are important optical films TiO2 exists in three different phases: anatase, rutile,
and brookite. Only anatase, rutile and amorphous film
have been observed in TiO2 thin films up to now [10].
*
Corresponding author. Tel.: þ86-10-62773925. The TiO2 films with different structure varied in optical
E-mail address: hyq99@[Link] (Y.-Q. Hou). and photocatalytic properties. Some researchers stated

0169-4332/$ – see front matter # 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0169-4332(03)00569-5
98 Y.-Q. Hou et al. / Applied Surface Science 218 (2003) 97–105

that the TiO2 film consisting of anatase and rutile phases Table 1
The parameters table of preparation TiO2 film by ac magnetron
with an appropriate ratio has the best photocatalytic
sputtering
activity [3]. So, it is important to optimize the pre-
paration process to obtain TiO2 film with appropriate Base pressure, P0 (Pa) 3.9  103
phase composition. And the key factors to influence Sputtering pressure, Pt (Pa) 2.0
Oxygen partial pressure PO2 (Pa) 0.2
the micro-structure of TiO2 film are substrate and Sputtering current I (A) 3.0
anneal temperature [10–13]. Therefore, in this paper, Substrate temperature Ts (8C) RT
the influence of annealing temperature on the micro-
structure, surface morphology and optical property of
TiO2 thin films prepared by mid-frequency ac mag-
netron sputtering technique has been studied. wafer and fused silica substrate. The average film
thickness of these specimens was about 340 nm. Then
these specimens have been annealed at various tem-
2. Experimental peratures: 300, 500, 700, 900 and 1100 8C in air for
1 h.
The TiO2 films were grown with a modified GDM-
450BN vacuum sputtering apparatus. The base pressure 3.2. X-ray diffraction measurements
of the deposition chamber was about 2:0  103 Pa.
The discharge of the sputtering can be sustained by a Fig. 1 shows the XRD patterns of TiO2 films depos-
3 kW ac power supply. The frequency of the ac power ited on fused silica substrate and annealed at different
supply was 20 kHz. The size of Ti target with the purity temperatures. As reference, the standard XRD patterns
of 99.99% was 120 mm  250 mm. The gas used in this of TiO2 powder in anatase and rutile phase are also
paper was the high pure argon (99.99%) and oxygen shown in Fig. 1(d) and (h).
(99.99%). Fig. 1(a) indicates the as-deposited TiO2 film is
The substrates used were 11.5 mm diameter  3 mm amorphous. Fig. 1(b) is the XRD pattern of TiO2 film
thick fused silica and silicon wafers (1 0 0). These specimen annealed at 300 8C. Some weak diffraction
substrates were cleaned by SSC-2 ultrasonic washer peaks can be seen in Fig. 1(b) and all of them appear in
with acetone, then rinsed with deionized water, and the positions corresponding the anatase structure. But
finally dried with clean heat wind. The film specimen these peaks are so weak and not completely, it can be
was annealed in an SX-2.5-10 box-type oven. thought that perhaps TiO2 film only changed partly
The thickness of the films was examined by L116B from amorphous to anatase.
ellipsometry. The crystalline structure of the films was Fig. 1(c) and (e) shows the XRD patterns of TiO2
measured using a D/max-RB X-ray diffractometer film annealed at 500 and 700 8C, respectively. These
(XRD). The surface morphology of the films has been patterns present clearly diffraction peaks of anatase
observed by atomic force microscopy (AFM) using a structure. And no rutile structure is observed in these
NanoScope III instrument with an etched silicon specimens. It can be concluded that the TiO2 film
cantilever. The ultraviolet and visible transmittance specimens annealed between 500 and 700 8C have
and reflectance spectra of TiO2 thin films on fused completely changed to anatase structure.
silica substrate were measured by a UV-2100S ultra- Contrasted with Fig. 1(d) and (h), it can be seen
violet spectrophotometer. that the diffraction peaks of anatase structure dis-
appeared, and only diffraction peaks of rutile struc-
ture are observed for TiO2 film annealed at 900 8C. It
3. Results and discussion can be seen from Fig. 1(g) that the TiO2 film
annealed at 1100 8C has more clear and more higher
3.1. Preparation of TiO2 film specimens diffraction peaks of rutile than that of 900 8C. So, it
can be suggested the phase transformation tempera-
With the technological parameters shown in Table 1, ture from anatase to rutile is between 700 and
the TiO2 film specimens were deposited on silicon 900 8C.
 Y.-Q. Hou et al. / Applied Surface Science 218 (2003) 97–105 99

Fig. 1. X-ray diffraction patterns of TiO2 thin films annealed at different temperatures and two typical X-ray spectra of TiO2: (a) as-deposited,
(b) 300 8C, (c) 500 8C, (d) anatase, (e) 700 8C, (f) 900 8C, (g) 1100 8C, (h) rutile.
100 Y.-Q. Hou et al. / Applied Surface Science 218 (2003) 97–105

3.3. Surface morphologies observed by AFM 4.386 nm when the annealing temperature increases
before 700 8C. When the temperature is higher than
The surface morphologies of TiO2 films deposited 900 8C, the rms value increases smartly and reaches
on silicon wafers were observed by AFM and the 43.487 nm for 1100 8C. The reason of the increase of
influence of annealing temperature on them has been roughness is the phase change and the growth of grain
studied. The surface morphology pictures of TiO2 size.
films are shown in Fig. 2. Fig. 2(a) shows the surface
morphology of as-deposited TiO2 film and column- 3.4. Transmittance and reflectance spectra of TiO2
like structure is found. The diameter of these column- films
like grains is about 30–50 nm. The surface of TiO2
film is fine and compact. Fig. 4 shows the transmittance spectra in ultraviolet
Fig. 2(b) is the surface morphology picture of TiO2 and visible region of fused silica substrate and TiO2
film specimen annealed at 300 8C. Some column-like films annealed at different temperatures. It can be seen
crystal grains of 100 nm in diameter appeared in it. that the transmittance of the fused silica substrate is
From Fig. 1(b), these grains can be confirmed as very high during the whole ultraviolet and visible
anatase structure. But most of the grains in film should region. In visible region optical property of as-depos-
still remained as amorphous. Fig. 2(c) and (d) shows ited TiO2 film is perfect and obvious absorption edge
the surface morphology picture of TiO2 film annealed is observed at 380 nm. When TiO2 film is annealed
at 500 and 700 8C, respectively. In Fig. 2(c), larger under lower temperature (T < 900 8C), the transmit-
anatase crystal grains are observed and the differ- tance of the TiO2 films decreases slightly. In visible
ence between the large and small grains is still region, the average transmittance of TiO2 film
obviously. In Fig. 2(d), the diameter of column-like annealed at 700 8C is higher than 70%. When the
grain is almost the same. Most of them is about annealing temperature is higher than 900 8C, the
50–100 nm. The surface of TiO2 film annealed at transmittance of TiO2 film decreases sharply and
700 8C is very similar to the as-deposited TiO2 film. the absorption edge in 380 nm is not clear. The
On the other hand, no rutile structure is found when transmittance of TiO2 film annealed at 1100 8C is
annealed at 700 8C. very low and mostly lower than 20%.
It can be seen that when the temperature reaches The reflectance spectra in ultraviolet and visible
900 8C (see Fig. 2(e)), there is a distinct change of region of fused silica substrate and TiO2 films
surface morphology. Fig. 2(e) shows that previously annealed at different temperatures are also obtained.
observed column-like nodules, now have facets and For lower annealing temperature (<1100 8C), the
change to nubbly. In addition, the size of the particles shapes of reflectance curves of TiO2 films are similar
increases dramatically up to 300–500 nm. More keen- and the interference fringes caused by the high refrac-
edged grain can be observed in Fig. 2(e) and they seem tive index of TiO2 films are very clear. In addition, the
to be less coalesced than that of being annealed under reflectance of TiO2 films changed a little, but not
lower temperature. Form Fig. 1, it can be conclude that regularly. The peak values of reflectance curves
TiO2 film annealed at 900 8C has changed into rutile increased slightly with the increase of annealing tem-
structure completely. So, the surface morphology also perature except 1100 8C. The reflectance of TiO2 film
changed obviously. Annealed at 1100 8C, TiO2 film annealed at 1100 8C is also very weak and mostly
(see Fig. 2(f)) shows perfect order arranged morphol- lower than 10%.
ogy and its grain size exceeds 1–3 mm. It can be easily Since the optical transmission of TiO2 film annealed
distinguished that large grains well crystallized in at 900 and 1100 8C is too weak and the interference
rutile structure and separated. fringes disappear in the visible region. Only the optical
In order to support the AFM observation, rms and properties of TiO2 films annealed under lower tem-
Ra roughness measurements of TiO2 films have been perature were investigated in this paper. The refractive
carried out. As shown in Fig. 3, the rms and Ra follow a indices and extinction coefficients of TiO2 films were
similar evolution as previous microscopic observa- calculated from the transmittance and reflectance
tion. The rms values increased slowly from 2.382 to spectra and discussed in Section 3.5.
 Y.-Q. Hou et al. / Applied Surface Science 218 (2003) 97–105 101

Fig. 2. Surface morphologies by AFM of titanium oxide films annealed at different temperatures: (a) as-deposited, (b) 300 8C, (c) 500 8C, (d)
700 8C, (e) 900 8C, (f) 1100 8C.
102 Y.-Q. Hou et al. / Applied Surface Science 218 (2003) 97–105

Fig. 3. The influence of annealing temperature on roughness of TiO2 film.

3.5. Optical constants of TiO2 films curve, which can be written as TM and Tm, respectively.
For the region of transparent and weak absorption
In the paper, the refractive indices and extinction (annealed under lower temperature), the film refractive
coefficients of TiO2 films were calculated by the envel- index nf can be calculated from formula (1) [15]:
ope method [14,15] and experimental expression [16], rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
respectively. In Fig. 4, the envelopes can be drawn nf ¼ Nþ ðN 2  n2s Þ (1)
through the maxima and minima of the transmittance

Fig. 4. Transmittance spectra of TiO2 thin films annealed at different temperatures.

 Y.-Q. Hou et al. / Applied Surface Science 218 (2003) 97–105 103

where its extinction coefficient decreases obviously when

2 annealed at 300 and 500 8C. However, after annealed
TM  Tm ns þ 1
N ¼ 2ns þ ; at 700 8C, the extinction coefficient increases clearly,
TM Tm 2 especially in the visible region.
ns stands for the refractive index of substrate. So, although the transmittance of as-deposited
The extinction coefficient k can be obtained from TiO2 film is fairly good, its refractive index is a little
the experimental expression (2) [16]: low and some absorption has been observed. After
   annealed at 300 and 500 8C, the refractive index of
T l
k ¼ ln (2) TiO2 film increases meanwhile the extinction coeffi-
1  R 4pd
cient decreases. When the annealing temperature is
where R and T stand for the transmittance and reflec- high up to 700 8C, the extinction coefficient increases
tance of TiO2 film, l for the wavelength, and d for the a little and the transmittance deteriorates slowly.
thickness of TiO2 film. Comparatively, TiO2 film annealed at 500 8C has
Figs. 5 and 6 illustrate the evolution of refractive higher reflective index and higher transparency over
indices and extinction coefficients as a function of a wide spectral range, which means the film annealed
wavelength for TiO2 films annealed at different at 500 8C has the best optical property.
temperatures, obtained with the methods mentioned The evolution of the optical property can be
above. explained by the phase transformation and the growth
Fig. 5 shows that the refractive indices decrease of crystal grains. It has been known from XRD
with the increase of wavelength. Moreover, the refrac- patterns and AFM pictures that as-deposited TiO2 film
tive indices increase slightly with temperature and is amorphous, which often contains many structural
approach to the refractive index of bulk anatase. In defects. After annealed under lower temperature, the
Fig. 6, it can be seen that all the extinction coefficients TiO2 films become denser and change into anatase
decrease sharply with wavelength at the wavelength of structure. The structural defects in TiO2 films
380 nm, which is corresponding to the optical bandgap decreased and the crystal grains did not get very
of anatase. In addition, the extinction coefficient of coarse. So, the TiO2 film annealed at 500 8C has
as-deposited TiO2 film is higher than 0.015, and the best optical property. After that, the crystal grains

Fig. 5. The variation of refractive indices as a function of wavelength of TiO2 films annealed under different temperatures.
104 Y.-Q. Hou et al. / Applied Surface Science 218 (2003) 97–105

Fig. 6. The variation of extinction coefficients as a function of wavelength of TiO2 films annealed under different temperatures.

get bigger and coarser. The sudden decrease of trans- 5. Finer micro-structure in film is favorable to result
mission observed at 900 8C suggests that it might in a higher refractive index. And, the reductions of
attribute to the phase transformation, which also leads structural defects and roughness value decrease
to the increase of the extinction coefficient. extinction coefficient of TiO2 film effectively.

4. Conclusions Acknowledgements

1. The TiO2 thin film deposited at room temperature This work was financially supported by the Funda-
by mid-frequency ac magnetron sputtering is mental Research Fund of the School of Mechanical
amorphous. It has a column-like structure, and Engineering, Tsinghua University (985 Project).
the diameter of these grains is about 30–50 nm.
2. After annealed at 300 8C for 1 h, some column-
like crystal grains with anatase structure appeared References
in TiO2 film. The TiO2 film specimen annealed at
700 8C has changed into anatase structure com- [1] S.K. Zheng, T.M. Wang, G. Xiang, et al., Vacuum 62 (2001)
pletely. 361–366.
3. TiO2 film has changed into rutile structure [2] M. Radecka, K. Zakrzewska, H. Czternastek, et al., Appl.
Surf. Sci. 65 (1993) 227–234.
completely and its rms values increase dramati-
[3] D. Dumitriu, A.R. Bally, C. Ballif, et al., Appl. Catal. B:
cally when the film is annealed at 900 8C and Enviorn. 25 (2000) 83–92.
above. Annealed at 1100 8C, the grain size in film [4] S. Takeda, S. Suzuki, H. Odaka, et al., Thin Solid Films 392
can exceed to several micrometers. (2001) 338–344.
4. The refractive index of TiO2 thin film increases [5] F. Zhang, N. Huang, P. Yang, et al., Surf. Coat. Technol. 84
(1996) 476–479.
with annealing temperature and extinction coeffi-
[6] T. Watanabe, S. Fukayama, M. Miyauchi, et al., J. Sol–Gel
cient of film decreases a little during the lower Sci. Technol. 19 (2000) 71–76.
temperature anneal. TiO2 film annealed at 500 8C [7] O. Treichel, V. Kirchhoff, Surf. Coat. Technol. 123 (2000)
has a best optical property. 268–272.
 Y.-Q. Hou et al. / Applied Surface Science 218 (2003) 97–105 105

[8] G. Bräuer, M. Ruske, J. Szczyrbowski, et al., Vacuum 51 (4) [12] L.-J. Meng, M.P. dos Santos, Appl. Surf. Sci. 65 (1993) 235–
(1998) 655–659. 239.
[9] Y.-Q. Hou, D.-M. zhuang, D.-Q. Zhao, et al., in: J. Tang, C.- [13] M. Radecka, K. Zakrzewska, H. Czternastek, et al., Appl.
N. Xu, H. Li (Eds.), Advanced Photonic Sensors: Technology Surf. Sci. 65 (1993) 227–234.
and Applications, vol. 4220, SPIE, Houston, 2000, pp. 34–38. [14] D.P. Arndt, R.M.A. Azzam, J.M. Bennett, et al., Appl. Opt. 23
[10] P. Löbl, M. Huppertz, D. Mergel, Thin Solid Films 251 (1994) (20) (1984) 3571–3596.
72–79. [15] R. Swanepoel, J. Phys. E: Sci. Instrum. 16 (1983) 1214–1222.
[11] N. Martin, C. Rousselot, D. Rondor, et al., Thin Solid Films [16] J. Rodriguez, M. Gomez, J. Ederth, G.A. Niklasson, C.G.
300 (1997) 113–121. Granqvist, Thin Solid Films 365 (2000) 119–125.