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1457 - 1461
TiO2 thin films prepared by sol-gel method and by RF magnetron sputtering deposited on p-Si(111), n-GaAs(100), and glass
have been investigated by XRD, XPS and AFM techniques. The characteristics of the film: colour, adherence and
composition are presented in the case of thermal treatments (500 0C and 800 0C) for sol-gel deposited films as well as for
RF sputtering. The TiO2 plasma deposited film is uniform, homogeneous and stoichiometric.
Keywords: TiO2, sol-gel method, RF sputtering, XPS analysis, AFM analysis, TGA analysis
with acetyl acetone , stirring for 30 min. After adding The AFM analysis was performed on AFM system
acetic acid the final mixture was stirred for 30 min. at model NOMAD QUESANT Instrument Corporation
room temperature; the pH of the sols was ≤ 2. The (USA).
chemical prescription used the molar ratios nacac/nTi=0.3, 3. Results and discussion
nacetic acid/nTi=0.2 to get a stable sol of concentration 2.609
M. Thin films were fabricated in a process where the The TGA analysis of dried gel evidenced (Fig. 1) four
substrate to be coated is immersed in a liquid (sol) and temperature regions as follows: below 1000C, between 100
then is dried in a spinner with a well-defined speed at to 2750C, from 275 to 4130C and from 413 to 5460C. In
room temperature in air. There were deposited a sequence the first region the weight loss is the result of water
of 10 thin layers on cleaved substrates of p-Si(111), evaporation from the surface of TiO2 powder. The
n-GaAs (100) and glass .Between each deposition the thin temperature range (100-275)0C is related to the weight loss
film was dried at T=100 oC for t=20 min. The properties of from the evaporation of butanol, acetyl acetone and acetate
TiO2 sol-gel films were investigated by XRD, XPS and groups which is not a part of gel structure. The
AFM analyses after annealing at T=500 and 8000C in air. temperature range (275-413)0C is attributed to the loss of
The dried gel was obtained after heating at 1000C. butoxide, acetylacetonate and acetate groups from gel
Thereafter the gel was subjected to a Thermal Gravimetry structure. For temperatures up to 546 oC occurs the
Analysis (TGA) on a PYRIS DIAMOND TG/DTA-Perkin combustion of organic constituents in the gel and starts the
Elmer, temperature range (25-1500)0C. crystallization of the anatase form. After 5460C it does not
The XRD analysis was performed in a DRON 2.0 appear any thermal effect.
system in air with a beam current I=20 mA at an
accelerating voltage U=30 kV using Mo anticathode
(Kα1=1.5405Å).
The XPS spectra were obtained with VG ESCA 3
MKII Spectrometer using monochromatized Al kα
radiation (1486.6 eV) the analysis chamber was
maintained at ultra high vacuum (p~10-9 torr) and the
sample position was oriented at θ=450 in respect to the
analyzer. The XPS spectra were recorded with a 20 eV
window, 50 eV resolution and 256 channels recordance.
Data collection was made using a computer interface Fig. 1-TGA analysis of TiO2 dried gel.
digital pulse counting system. The spectra were processed
using SDP v2.3 software which allows smoothing and
deconvolution of the curve. The XRD analysis of sol-gel TiO2 thin films deposited
The RF plasma magnetron deposition was performed on glass and annealed at 5000C (Fig. 2) revealed a peak at
on a VARIAN R 3119- European certified. The deposition 250 attributed to anatase phase on the background of the
condition for a thickness of 50 nm TiO2 film were: oxygen glass amorphous phase. The TiO2 film deposited on glass
controlled atmosphere at a flow rate of 30 sccm monitories is semi-transparent and whitish. The adherence is good
by a ultraflo US mass flow controller model 80-5, vapor both on glass and on silicon. Regarding the modification
pressure 5×10-3 Torr and a deposition rate between of the substrate type the crystallization process does not
0.3-1Å/s. The TiO2 sputtered films deposited on p-Si(111) depend on the support and the anatase crystallization
and n-GaAs(100) were investigated by AFM analysis process begins at 4800C [5]. The XRD spectrum of
regarding the surface quality and by XPS for the surface TiO2/p-Si(111) annealed at 5000C presents peaks
composition corresponding to anatase form at 250 and 380 and a peak at
28 · 5 0 of silicon.
The XPS investigation at the surface of TiO2 films RX: U=14 kV, I=20 mA, P=280 W, Flod gun U=3 V,
deposited on p-Si(111), n-GaAs(100), and glass by sol-gel I=0.02 mA. As a general remarks, the C line is enhanced
method and RF magnetron sputtering put into evidence a due to air adsorption (after annealing at 800 oC). The
stoichiometric compound. For XPS analysis the binding organic part of the gel is decomposed, the signal of oxygen
energies were calibrated with reference to C 1s at 285 eV. arises from the line 532 eV corresponding to absorbed
The measurement conditions were p=10-9torr, Ume=3.2 kV, oxygen and the line 529.33 corresponds to TiO2. In
Properties of TiO2 thin films prepared by different techniques 1459
Ti 2p
O 1s
C 1s
concentration ratio of 33.5% to 66.5%. This suggests that 55000
the oxidation state of TiO2 may be obtained from spin- 45000
Ti 2p3
orbit splitting of 2P1/2 and 2P3/2 electron bands of titanium 35000
[1]. Regarding the signal arised from silicon, in the main
Ti 2s
Ti 2p1
25000
Ti Auger
Ti Auger
Ti Auger
O Auger
Auger
O Auger
C Auger
part it proceed from SiO2.
15000
3dC 2s
2s3p
Ti 3s
O loss
C loss
TiOx/pSi(111) System Name: XI ASCII
Ti
5000
OO2p
4s
Ti 2p Pass Energy: 100.00 eV
Ti
Charge Bias: 0.0 eV 1200 900 600 300 0
Counts 22 Feb 1906 Binding Energy, eV
Ti 2p
66.5% Ti 2p (A)
30000 33.5% Ti 2p (B) a
26000 A 459.08 eV 2.03 eV 20733.5 cts TiOx/nGaAS(100) System Name: XI ASCII
22000 B 464.70 eV 2.83 eV 10418.7 cts Ti 2p3 Ti 2p Pass Energy: 100.00 eV
Baseline: 468.29 to 455.90 eV Charge Bias: 0.0 eV
B
A
Ti 2p
65.0% Ti 2p (A)
10000 22000 35.0% Ti 2p (B)
6000 18000 A 457.21 eV 2.27 eV 16525.5 cts
Ti 2p3
B 462.88 eV 3.02 eV 8856.51 cts
B
2000 Baseline: 466.96 to 453.94 eV
14000
Chi square: 3.37732
470 466 462 458 454
Ti 2p1
Binding Energy, eV 10000
6000
a 2000
9000
In this study we deposited TiO2 thin films on p-
7000
Si(111) and n-GaAs(100) using radio-frequency (RF)
Ti 2p1
5000
magnetron sputtering in order to understand the role of
3000
different techniques on the quality of TiO2 films. The XPS
1000
analysis (Fig. 5) put into evidence a signal of O-1s from
470 466 462 458 454 TiO2/Si that arises from oxygen in oxide (530.79 eV) in a
Binding Energy, eV
proportion of 71.7% and from adsorbed oxygen
(532.00 eV) in a proportion of 28.3%. The titanium signal
b
from TiO2 is very clear (2P1/2 31.8 % and 2P3 68.2%) and
Fig. 3. XPS spectrum of Ti for TiO2 film (sol-gel) does not exist other compounds as e.g titanium oxide
annealed at 500 0C (a) and 800 0C (b). species (Fig. 5). The same observations are consistent also
with TiO2 film on GaAs-for titanium signal the
composition indicates a clearly and accurate TiO2
For TiO2 sol-gel thin film deposited on n-GaAs (100) stoichiometric compound (2P1/2 28.4%, 2P3/2 71.6%)
and annealed at 800 oC the general XPS spectrum is shown For RF magnetron sputtering of TiO2 films deposited
in Fig. 4 (a). The spectrum is focused on the peak lines Ti- on Si and GaAs the AFM characteristics are presented in
Auger, Ti-2s, Ti-2P1/2, Ti-2P1/2, O-Auger, C-1s, O-1s; in Fig. 6. For Silicon the wafer surface was not prepared at a
the range (0-450)eV the binding energies are related to the optical quality. The surface area investigated was 5µm
Auger lines for Ga and As and the lines for Ga-3d and As- ×5µm and RMS diagram was 3.587 nm. For TiO2/Si film
3d. For titanium lines the concentration ratio 2P1/2to 2P3/2
the RMS deviation is 10.69 nm and mean deviation is
is 35% to 65%. The sample TiO2 /n-GaAs has at its surface
0.007 nm TiO2 film of a thickness 50 nm is uniform with a
an uniform white film, the sample TiO2/p-Si is a non -
uniform film part, and for TiO2/glass sample, the film is average height of 26.65 nm. For TiO2 films at an
uniform, transparent but with poor adherence. In the equivalent thickness of λ/4 at 1µm, the initial surface
oxygen signal of TiO2/glass annealed at 500 oC, the peak morphology is changed. It is observed a cluster structure
from 529.64 eV is attributed to TiO2 in a preparation of of the semi arranged layer. Optical quality of the deposited
87.6%. Titanium peak positions corresponds to the layers is influenced by the wafer surface quality.
oxidation state Ti4+ [1].
1460 F. Ungureanu, R. Medianu, R. V. Ghita, C. C. Negrila, P. Ghita, A. S. Manea, M. F. Lazarescu
A
Composition Table
Ti 2p
45000 68.2% Ti 2p (A)
31.8% Ti 2p (B)
Ti 2p3
B 463.51 eV 2.90 eV 15009.5 cts
Baseline: 467.35 to 454.72 eV
B
25000 Chi square: 5.84853
Ti 2p1
15000
5000
Counts
Charge Bias: 0.0 eV
22 Feb 1906
GaAs wafer
A
Composition Table
45000 71.6% Ti 2p (A)
Ti 2p
28.4% Ti 2p (B)
35000 A 459.29 eV 2.02 eV 31971 cts
Ti 2p3
15000
5000
50 nm TiO2/Si
Fig. 7. AFM image of TiO2/n-GaAs(sol-gel) annealed at 800 oC.
Properties of TiO2 thin films prepared by different techniques 1461
4. Conclusions References
In the present study the principal characteristics of [1] M. Z.Atashbar, H. T.Sun, B. Gong, W. Wlodarski,
TiO2 films deposited on p-Si(111), n-GaAs(100) by sol-gel R. Lamb, Thin Solid Films 326, 238 (1998).
techniques and by RF magnetron sputtering techniques [2] T. Takeuchi, Sens Actuators, 14, 109 (1988).
were investigated. The estimated thickness of sol-gel films [3] W. Gopel, G.Roker, R. Feierabend, Phys. Rev B
was <1µm obtained by successive deposition of 10 layers 28(6), 3427 (1993).
from a titanium n-butoxide sol in the presence of acetic [4] Cheol Ho Heo, Soon-Bo Lee, Jin-Hyo Boo, Thin Solid
acid. XPS analysis led to a detailed knowledge about the Films, 475, 183 (2005).
chemical properties of the film samples. TiO2 films [5] C. Legrand-Buscema, C. Malibert, S. Bach, Thin Solid
deposited by both techniques are found to be Films, 418, 79 (2002).
stoichiometric. Surface quality investigated by AFM [6] Gian Piero Banfi, V. Degiorgio, D. Ricard, Adv. Phys
shows an uniform aspect for TiO2 deposited by RF 47, 447 (1998).
sputtering. The XRD analysis performed on TiO2 sol-gel [7] F. Burmeister, C. Schafle, B. Kielhofer, C. Bechinger,
films put into evidence the presence of anatase phase on J. Boneberg, P. Leiderer, Adv. Mater. 10, 495 (1998).
glass and Si substrates. The TGA analysis recorded the
different stages to the route of crystallization of titanium
oxide. _________________________
*
Corresponding author: uflori77@yahoo.com
ghitar@infim.ro