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International Journal of Civil Engineering and Technology (IJCIET)
Volume 10, Issue 1, January 2019, pp.227–232, Article ID: IJCIET_10_01_022
Available online at http://www.iaeme.com/IJCIET/issues.asp?JType=IJCIET&VType=10&IType=1
ISSN Print: 0976-6308 and ISSN Online: 0976-6316
©IAEME Publication Scopus Indexed
INVESTIGATION OF INTERNAL
THERMOELASTIC STRESSES IN TIO2 FILM ON
SAPPHIRE SUBSTRATE
Yu. V. Klunnikova
Southern Federal University, 347928, Taganrog, Nekrasovsky, 44, Russia
S. P. Malyukov
Southern Federal University, 347928, Taganrog, Nekrasovsky, 44, Russia
A. V. Sayenko
Southern Federal University, 347928, Taganrog, Nekrasovsky, 44, Russia
Yu.N.Biyatenko
Southern Federal University, 344090, Rostov-on-Don, Milchakova 10, Russia
ABSTRACT
We investigate thermoelastic stresses in titanium dioxide films on a sapphire
substrate that arise during thermal annealing. The effect of thermal processes on
thermoelastic stresses in titanium dioxide films has been studied experimentally. The
obtained experimental results are in good agreement with the theoretical calculations
of mechanical stresses in a titanium dioxide film.
Keywords: Devices, Film, Sapphire Substrate, Thermal Annealing, Thermoelastic
Stresses.
Cite this Article: Yu. V. Klunnikova, S. P. Malyukov, A. V. Sayenko and
Yu.N.Biyatenko, Investigation of Internal Thermoelastic Stresses In Tio2 Film On
Sapphire Substrate, International Journal of Civil Engineering and Technology
(IJCIET), 10 (1), 2019, pp. 227–232.
http://www.iaeme.com/IJCIET/issues.asp?JType=IJCIET&VType=10&IType=1
1. INTRODUCTION
The possibility of reception thin films on dielectric and semiconductor substrates gives wide
opportunities for the design of functional devices (photoelectric converters and sensitive
elements of gas sensors). Nowadays the interest in studying the properties of thin films has
increased in micro- and nanoelectronics. There are the most widely spread gas sensitive
materials such as oxides of titanium (TiO2), tin (SnO2), tungsten (WO3), zinc (ZnO), indium
(In2O3), copper (Cu2O, CuO), iron (Fe2O3), their combinations and others. One of the
Yu. V. Klunnikova, S. P. Malyukov, A. V. Sayenko and Yu.N.Biyatenko
http://www.iaeme.com/IJCIET/index.asp 228 editor@iaeme.com
important features of gas sensors based on titanium dioxide (TiO2) is the possibility of their
operation at high temperatures due to the film high chemical stability [1-4].
2. METHOD OF TITANIUM DIOXIDE FILMS FORMATION
The formation of titanium dioxide films on sapphire substrate is accompanied by the
appearance of thermoelastic stresses due to the difference in thermal expansion coefficients of
the film and substrate, which can cause destruction of the film and affect the operation of the
devices functional elements based on this film.
The purpose of this work is to study the formation of thin films of titanium dioxide and to
estimate the level of thermoelastic stresses arising in the structures of titanium dioxide (TiO2)
film – sapphire substrate. The mechanisms of the film structures formation play an important
role in the processes of the appearance and relaxation of internal thermoelastic stresses.
The centrifugation method and then annealing in a muffle furnace were used for titanium
dioxide film formation on sapphire substrate [3-4]. We clean sapphire substrate in an
ultrasonic bath for 15 minutes in water and then in isopropanol. The titanium dioxide layer
was deposited from 0.3 M titanium diisopropoxidebis (acetylacetonate) (75 wt. % in
isopropanol) in 1-butanol (99.8 %, Sigma-Aldrich) on sapphire substrate with 0.43 mm thick
by centrifugation (SPIN NXG-P1 centrifuge, rotor speed 4000 rpm, deposition time 40
seconds). Titanium dioxide film drying was carried out in furnace at 125 0
C for 5 minutes and
then annealed at 500 0
C in muffle furnace for 30 minutes. Figure 1 shows the technological
process of film annealing in a muffle furnace (heating and cooling). The titanium dioxide film
on sapphire substrate was held at 200 0
C for 10 minutes.
Figure 1 Technological process of titanium dioxide film annealing in a muffle furnace
The use of sapphire substrate allows further annealing of the gas sensitive material,
because the sapphire has the high adhesion strength to the gas sensitive material, the high
melting point, chemical and radiation resistance, high hardness and transparency, which leads
to improved quality and stability of the gas sensitive material [5-8].
3. INVESTIGATION OF TITANIUM DIOXIDE FILMS PROPERTIES
The obtained films of titanium dioxide on sapphire substrate were investigated by atomic
force microscopy (AFM). The statistical processing of AFM data was performed using a
software package Image Analysis 3.5. The results of the studies (Figure 2) showed that the
Investigation of Internal Thermoelastic Stresses In Tio2 Film On Sapphire Substrate
http://www.iaeme.com/IJCIET/index.asp 229 editor@iaeme.com
obtained titanium dioxide films on sapphire substrate are uniform, while the crystal diameter
values are in the range up to 200 ± 250 nm.
A
B
Figure 2AFM image (phase contrast) of titanium dioxide film on sapphire substrate
We carried out the experimental studies to measure thermal stresses in thin TiO2 films on
the Tencor FLX-2320 (Japan) in the laboratories of «Piezopribor» research center (Russia,
Rostov-on-Don). The basis of this study is the technique for measuring the surface stresses of
thin films by estimating the change in the radius of curvature of the substrate caused by the
influence of a thin film formed on it. The deflection of titanium dioxide thin film on sapphire
substrate is shown in Figure 3. The calculation results of thermoelastic stresses obtained from
these studies are shown in Figure 4. 3D map of thermoelastic stresses of titanium dioxide thin
film on sapphire substrate is presented in Figure 5.
Thermoelastic stresses depend on the parameters and conditions of the film formation
process (Figure 1). Their value can be varied to the required one by changing various
parameters and factors of film formation process (annealing temperature, centrifugation speed
and time).
Figure 3 3D map of the deflection of titanium dioxide film with a thickness of about 100 nm on
sapphire substrate (0.43 mm thick)
Yu. V. Klunnikova, S. P. Malyukov, A. V. Sayenko and Yu.N.Biyatenko
http://www.iaeme.com/IJCIET/index.asp 230 editor@iaeme.com
Figure 4Study of thermoelastic stresses in titanium dioxide films with a thickness about 100 nm on
sapphire substrate (0.43 mm thick)
Figure 53D map of thermoelastic stresses of titanium dioxide thin film on sapphire substrate
The temperature coefficient of linear expansion of titanium dioxide films is 7,4·10–6
1/0
С,
which is higher than sapphire crystal one [4]. So the thermal stresses in titanium dioxide on
sapphire substrate are tensile.
Investigations of the temperature effect on thermoelastic stresses in titanium dioxide films
on sapphire substrate showed that when we heat the structure to 40 0
C, the value of the
thermoelastic stress is at the same level (about 1.1 GPa) (Figure 6). A further temperature
increase leads to growth of the value of thermoelastic stresses in titanium dioxide films on
sapphire substrate, which may have a negative effect on the characteristics of devices
functional elements based on these films.
Investigation of Internal Thermoelastic Stresses In Tio2 Film On Sapphire Substrate
http://www.iaeme.com/IJCIET/index.asp 231 editor@iaeme.com
Figure 63D map of thermoelastic stresses of titanium dioxide thin film on sapphire substrate
The resulting thermal stresses σT for a biaxial symmetric stressed state are determined by
the relation [9]:
( ) (1)
where is the Young's modulus of film; is the Poisson's ratios of film; , are the
coefficients of linear expansion of the film and substrate; is the temperature change.
The calculation results of thermoelastic stresses in titanium dioxide films on sapphire
substrate are shown in Figure 7.
Figure 7 Dependence of thermoelastic stresses on temperatures in titanium dioxide films
The stresses in titanium dioxide films with 100 nm thick on sapphire substrate were about
1 – 3 GPa from the results of measurements and calculations.
4. CONCLUSION
The titanium dioxide thin films on sapphire substrate were obtained by centrifugation using a
precursor diisopropoxide titanium bis (acetylacetonate), which can find wide application for
gas sensitive sensors and photoelectric converters. We investigate of thermoelastic stresses in
thin TiO2 films on sapphire substrate arising because of the difference in values of film and
Yu. V. Klunnikova, S. P. Malyukov, A. V. Sayenko and Yu.N.Biyatenko
http://www.iaeme.com/IJCIET/index.asp 232 editor@iaeme.com
substrate thermal expansion coefficients. Theoretical and experimental studies have shown
that tensile thermal stresses are formed during titanium dioxide film obtaining on sapphire
substrate. We study the temperature influence on thermoelastic stresses in titanium dioxide
films. It is determined that at a heating temperature of the structure up to 40 0
C the
thermoelastic stresses value is at the same level (about 1.1 GPa).
The results of experimental studies of thermoelastic stresses in titanium dioxide films on
sapphire substrate accord with theoretical calculations for film thickness about 100 nm.
ACKNOWLEDGEMENTS
This research is supported by the Federal Target Program No. 14.587.21.0025, the project ID
is RFMEFI58716X0025.
REFERENCES
[1] Gaskov,A.M.,Rumyantseva, M. N., Materials Selection for Solid-state Gas Sensors,
Inorganic Materials, 3, 2000, pp. 369–378.
[2] Buslov, V.,Kozhevnikov, V., Kulikov, D.,Rembesa, S.,Russkiy, D., Semiconductor
Sensing Elements for Gas Sensors and Warning Systems, Modern electronics,7, 2008, pp.
22–27.
[3] Choroshich,V.M.,Belous,V. A., Titanium Dioxide Films for Photocatalysis and Medicine,
FIP, 7, 2009, pp. 223–238.
[4] Seo, M.-H., Yuasa, M.,Kida, T., Huh,J.-S.,Yamazoe, N., Shimanoe, K., Detection of
Organic Gases Using TiO2Nanotube-based Gas Sensors, Procedia Chemistry, 1, 2009, pp.
192–195.
[5] Dobrovinskaya, E.R.,Lytvynov, L.A., Pishchik, V.V. Sapphire. Material, Manufacturing,
Applications. New York:Springer, 2009, pp. 65.
[6] Bogdanov,Yu.,Kochemasov, V., Khasyanova, E., Inorganic Substrates: Characteristics,
Selection Criteria, Printed Wiring, 1, 2014, pp. 204–216.
[7] Akselrod,M.S., Bruni, F. J., Modern Trends in Crystal Growth and New Applications of
Sapphire, Journal of Crystal Growth, 360(1), 2012, pp. 134–145.
[8] Cherednichenko, D. I., Malyukov, S. P., Klunnikova, Yu.V., Heat-physical Processes at
the Sapphire Crystals Growth by Horizontal Directed Crystallization, In: Structure,
Technology and Applications. USA, Nova Science Publishers, 2013, pp. 101–118.
[9] Tamulevicius, S, Stress and Strain in the Vacuum Deposited Thin Films, Vacuum, 51(2),
1998, pp. 127–139.
[10] Morozova, N.S., Tseunov, A.P.,Ermolovich, I.M.,Electrical Conductivity of Titanium
Oxide Thin Films Obtained by Medium-Frequency Magnetron Sputtering, XV
International Scientific and Practical Conference of Students, Post-Graduates and Young
Scientists «Modern Techniques and Technologies”, 2009, pp. 86–88.

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Ijciet 10 01_022

  • 1. http://www.iaeme.com/IJMET/index.asp 227 editor@iaeme.com International Journal of Civil Engineering and Technology (IJCIET) Volume 10, Issue 1, January 2019, pp.227–232, Article ID: IJCIET_10_01_022 Available online at http://www.iaeme.com/IJCIET/issues.asp?JType=IJCIET&VType=10&IType=1 ISSN Print: 0976-6308 and ISSN Online: 0976-6316 ©IAEME Publication Scopus Indexed INVESTIGATION OF INTERNAL THERMOELASTIC STRESSES IN TIO2 FILM ON SAPPHIRE SUBSTRATE Yu. V. Klunnikova Southern Federal University, 347928, Taganrog, Nekrasovsky, 44, Russia S. P. Malyukov Southern Federal University, 347928, Taganrog, Nekrasovsky, 44, Russia A. V. Sayenko Southern Federal University, 347928, Taganrog, Nekrasovsky, 44, Russia Yu.N.Biyatenko Southern Federal University, 344090, Rostov-on-Don, Milchakova 10, Russia ABSTRACT We investigate thermoelastic stresses in titanium dioxide films on a sapphire substrate that arise during thermal annealing. The effect of thermal processes on thermoelastic stresses in titanium dioxide films has been studied experimentally. The obtained experimental results are in good agreement with the theoretical calculations of mechanical stresses in a titanium dioxide film. Keywords: Devices, Film, Sapphire Substrate, Thermal Annealing, Thermoelastic Stresses. Cite this Article: Yu. V. Klunnikova, S. P. Malyukov, A. V. Sayenko and Yu.N.Biyatenko, Investigation of Internal Thermoelastic Stresses In Tio2 Film On Sapphire Substrate, International Journal of Civil Engineering and Technology (IJCIET), 10 (1), 2019, pp. 227–232. http://www.iaeme.com/IJCIET/issues.asp?JType=IJCIET&VType=10&IType=1 1. INTRODUCTION The possibility of reception thin films on dielectric and semiconductor substrates gives wide opportunities for the design of functional devices (photoelectric converters and sensitive elements of gas sensors). Nowadays the interest in studying the properties of thin films has increased in micro- and nanoelectronics. There are the most widely spread gas sensitive materials such as oxides of titanium (TiO2), tin (SnO2), tungsten (WO3), zinc (ZnO), indium (In2O3), copper (Cu2O, CuO), iron (Fe2O3), their combinations and others. One of the
  • 2. Yu. V. Klunnikova, S. P. Malyukov, A. V. Sayenko and Yu.N.Biyatenko http://www.iaeme.com/IJCIET/index.asp 228 editor@iaeme.com important features of gas sensors based on titanium dioxide (TiO2) is the possibility of their operation at high temperatures due to the film high chemical stability [1-4]. 2. METHOD OF TITANIUM DIOXIDE FILMS FORMATION The formation of titanium dioxide films on sapphire substrate is accompanied by the appearance of thermoelastic stresses due to the difference in thermal expansion coefficients of the film and substrate, which can cause destruction of the film and affect the operation of the devices functional elements based on this film. The purpose of this work is to study the formation of thin films of titanium dioxide and to estimate the level of thermoelastic stresses arising in the structures of titanium dioxide (TiO2) film – sapphire substrate. The mechanisms of the film structures formation play an important role in the processes of the appearance and relaxation of internal thermoelastic stresses. The centrifugation method and then annealing in a muffle furnace were used for titanium dioxide film formation on sapphire substrate [3-4]. We clean sapphire substrate in an ultrasonic bath for 15 minutes in water and then in isopropanol. The titanium dioxide layer was deposited from 0.3 M titanium diisopropoxidebis (acetylacetonate) (75 wt. % in isopropanol) in 1-butanol (99.8 %, Sigma-Aldrich) on sapphire substrate with 0.43 mm thick by centrifugation (SPIN NXG-P1 centrifuge, rotor speed 4000 rpm, deposition time 40 seconds). Titanium dioxide film drying was carried out in furnace at 125 0 C for 5 minutes and then annealed at 500 0 C in muffle furnace for 30 minutes. Figure 1 shows the technological process of film annealing in a muffle furnace (heating and cooling). The titanium dioxide film on sapphire substrate was held at 200 0 C for 10 minutes. Figure 1 Technological process of titanium dioxide film annealing in a muffle furnace The use of sapphire substrate allows further annealing of the gas sensitive material, because the sapphire has the high adhesion strength to the gas sensitive material, the high melting point, chemical and radiation resistance, high hardness and transparency, which leads to improved quality and stability of the gas sensitive material [5-8]. 3. INVESTIGATION OF TITANIUM DIOXIDE FILMS PROPERTIES The obtained films of titanium dioxide on sapphire substrate were investigated by atomic force microscopy (AFM). The statistical processing of AFM data was performed using a software package Image Analysis 3.5. The results of the studies (Figure 2) showed that the
  • 3. Investigation of Internal Thermoelastic Stresses In Tio2 Film On Sapphire Substrate http://www.iaeme.com/IJCIET/index.asp 229 editor@iaeme.com obtained titanium dioxide films on sapphire substrate are uniform, while the crystal diameter values are in the range up to 200 ± 250 nm. A B Figure 2AFM image (phase contrast) of titanium dioxide film on sapphire substrate We carried out the experimental studies to measure thermal stresses in thin TiO2 films on the Tencor FLX-2320 (Japan) in the laboratories of «Piezopribor» research center (Russia, Rostov-on-Don). The basis of this study is the technique for measuring the surface stresses of thin films by estimating the change in the radius of curvature of the substrate caused by the influence of a thin film formed on it. The deflection of titanium dioxide thin film on sapphire substrate is shown in Figure 3. The calculation results of thermoelastic stresses obtained from these studies are shown in Figure 4. 3D map of thermoelastic stresses of titanium dioxide thin film on sapphire substrate is presented in Figure 5. Thermoelastic stresses depend on the parameters and conditions of the film formation process (Figure 1). Their value can be varied to the required one by changing various parameters and factors of film formation process (annealing temperature, centrifugation speed and time). Figure 3 3D map of the deflection of titanium dioxide film with a thickness of about 100 nm on sapphire substrate (0.43 mm thick)
  • 4. Yu. V. Klunnikova, S. P. Malyukov, A. V. Sayenko and Yu.N.Biyatenko http://www.iaeme.com/IJCIET/index.asp 230 editor@iaeme.com Figure 4Study of thermoelastic stresses in titanium dioxide films with a thickness about 100 nm on sapphire substrate (0.43 mm thick) Figure 53D map of thermoelastic stresses of titanium dioxide thin film on sapphire substrate The temperature coefficient of linear expansion of titanium dioxide films is 7,4·10–6 1/0 С, which is higher than sapphire crystal one [4]. So the thermal stresses in titanium dioxide on sapphire substrate are tensile. Investigations of the temperature effect on thermoelastic stresses in titanium dioxide films on sapphire substrate showed that when we heat the structure to 40 0 C, the value of the thermoelastic stress is at the same level (about 1.1 GPa) (Figure 6). A further temperature increase leads to growth of the value of thermoelastic stresses in titanium dioxide films on sapphire substrate, which may have a negative effect on the characteristics of devices functional elements based on these films.
  • 5. Investigation of Internal Thermoelastic Stresses In Tio2 Film On Sapphire Substrate http://www.iaeme.com/IJCIET/index.asp 231 editor@iaeme.com Figure 63D map of thermoelastic stresses of titanium dioxide thin film on sapphire substrate The resulting thermal stresses σT for a biaxial symmetric stressed state are determined by the relation [9]: ( ) (1) where is the Young's modulus of film; is the Poisson's ratios of film; , are the coefficients of linear expansion of the film and substrate; is the temperature change. The calculation results of thermoelastic stresses in titanium dioxide films on sapphire substrate are shown in Figure 7. Figure 7 Dependence of thermoelastic stresses on temperatures in titanium dioxide films The stresses in titanium dioxide films with 100 nm thick on sapphire substrate were about 1 – 3 GPa from the results of measurements and calculations. 4. CONCLUSION The titanium dioxide thin films on sapphire substrate were obtained by centrifugation using a precursor diisopropoxide titanium bis (acetylacetonate), which can find wide application for gas sensitive sensors and photoelectric converters. We investigate of thermoelastic stresses in thin TiO2 films on sapphire substrate arising because of the difference in values of film and
  • 6. Yu. V. Klunnikova, S. P. Malyukov, A. V. Sayenko and Yu.N.Biyatenko http://www.iaeme.com/IJCIET/index.asp 232 editor@iaeme.com substrate thermal expansion coefficients. Theoretical and experimental studies have shown that tensile thermal stresses are formed during titanium dioxide film obtaining on sapphire substrate. We study the temperature influence on thermoelastic stresses in titanium dioxide films. It is determined that at a heating temperature of the structure up to 40 0 C the thermoelastic stresses value is at the same level (about 1.1 GPa). The results of experimental studies of thermoelastic stresses in titanium dioxide films on sapphire substrate accord with theoretical calculations for film thickness about 100 nm. ACKNOWLEDGEMENTS This research is supported by the Federal Target Program No. 14.587.21.0025, the project ID is RFMEFI58716X0025. REFERENCES [1] Gaskov,A.M.,Rumyantseva, M. N., Materials Selection for Solid-state Gas Sensors, Inorganic Materials, 3, 2000, pp. 369–378. [2] Buslov, V.,Kozhevnikov, V., Kulikov, D.,Rembesa, S.,Russkiy, D., Semiconductor Sensing Elements for Gas Sensors and Warning Systems, Modern electronics,7, 2008, pp. 22–27. [3] Choroshich,V.M.,Belous,V. A., Titanium Dioxide Films for Photocatalysis and Medicine, FIP, 7, 2009, pp. 223–238. [4] Seo, M.-H., Yuasa, M.,Kida, T., Huh,J.-S.,Yamazoe, N., Shimanoe, K., Detection of Organic Gases Using TiO2Nanotube-based Gas Sensors, Procedia Chemistry, 1, 2009, pp. 192–195. [5] Dobrovinskaya, E.R.,Lytvynov, L.A., Pishchik, V.V. Sapphire. Material, Manufacturing, Applications. New York:Springer, 2009, pp. 65. [6] Bogdanov,Yu.,Kochemasov, V., Khasyanova, E., Inorganic Substrates: Characteristics, Selection Criteria, Printed Wiring, 1, 2014, pp. 204–216. [7] Akselrod,M.S., Bruni, F. J., Modern Trends in Crystal Growth and New Applications of Sapphire, Journal of Crystal Growth, 360(1), 2012, pp. 134–145. [8] Cherednichenko, D. I., Malyukov, S. P., Klunnikova, Yu.V., Heat-physical Processes at the Sapphire Crystals Growth by Horizontal Directed Crystallization, In: Structure, Technology and Applications. USA, Nova Science Publishers, 2013, pp. 101–118. [9] Tamulevicius, S, Stress and Strain in the Vacuum Deposited Thin Films, Vacuum, 51(2), 1998, pp. 127–139. [10] Morozova, N.S., Tseunov, A.P.,Ermolovich, I.M.,Electrical Conductivity of Titanium Oxide Thin Films Obtained by Medium-Frequency Magnetron Sputtering, XV International Scientific and Practical Conference of Students, Post-Graduates and Young Scientists «Modern Techniques and Technologies”, 2009, pp. 86–88.