Deposition of TiO₂ thin films using atmospheric dielectric barrier discharge
In this paper the influence of precursor (titanium tetraisopropoxide (TTIP)) temperature, precursor and gas flow rates on the surface properties of TiO₂ thin films deposited by atmospheric dielectric barrier discharge (ADBD) chemical vapour deposition (CVD) were investigated. Argon was used as worki...
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Національний науковий центр «Харківський фізико-технічний інститут» НАН України
2008
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| Cite this: | Deposition of TiO₂ thin films using atmospheric dielectric barrier discharge / Y. Klenko, J. Píchal // Вопросы атомной науки и техники. — 2008. — № 6. — С. 177-179. — Бібліогр.: 12 назв. — англ. |
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| author | Klenko, Y. Píchal, J. |
| author_facet | Klenko, Y. Píchal, J. |
| citation_txt | Deposition of TiO₂ thin films using atmospheric dielectric barrier discharge / Y. Klenko, J. Píchal // Вопросы атомной науки и техники. — 2008. — № 6. — С. 177-179. — Бібліогр.: 12 назв. — англ. |
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| description | In this paper the influence of precursor (titanium tetraisopropoxide (TTIP)) temperature, precursor and gas flow rates on the surface properties of TiO₂ thin films deposited by atmospheric dielectric barrier discharge (ADBD) chemical vapour deposition (CVD) were investigated. Argon was used as working gas. Influence of O₂ used as oxidizer was evaluated for determination of hydrophilicity of the films. Surface morphology of the thin TiO2 films deposited on glass substrates was studied by the atomic force microscopy (AFM) and water contact angle (CA) measurement. CA tests proved wettability improvement in experiments with oxygen addition.
Було досліджено вплив температури прекурсору тетраізопропоксиду титану, швидкості потоку прекурсора і газу на поверхневі властивості плівок діоксиду титану, нанесених в атмосферному діелектричному бар'єрному розряді методом хімічного осадження з газової фази. Аргон був використаний як робочий газ. Також досліджувався вплив кисню як окислювача на гідрофільність плівок. Морфологія поверхні тонких плівок, нанесених на скляні підкладки, була досліджена атомно-силовою мікроскопією і виміром контактного кута. Тестування методом виміру контактного кута довело поліпшення гідрофільності плівок в експериментах, проведених з додаванням кисню.
Было исследовано влияние температуры прекурсора тетраизопропоксида титана, скорости потока прекурсора и газа на поверхностные свойства пленок диоксида титана, нанесенных в атмосферном диэлектрическом барьерном разряде методом химического осаждения из газовой фазы. Аргон был использован как рабочий газ. Также исследовалось влияние кислорода как окислителя на гидрофильность пленок. Морфология поверхности тонких пленок TiO₂, нанесенных на стеклянные подложки, была исследована атомно-силовой микроскопией и измерением контактного угла. Тестирование методом измерения контактного угла доказало улучшение гидрофильности пленок в экспериментах, проведенных с дополнительной подачей кислорода.
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DEPOSITION OF TiO2 THIN FILMS USING ATMOSPHERIC
DIELECTRIC BARRIER DISCHARGE
Y. Klenko, J. Píchal
Czech Technical University, Faculty of Electrical Engineering, Department of Physics,
Technická 2, 166 27 Prague, Czech Republic
In this paper the influence of precursor (titanium tetraisopropoxide (TTIP)) temperature, precursor and gas flow
rates on the surface properties of TiO2 thin films deposited by atmospheric dielectric barrier discharge (ADBD)
chemical vapour deposition (CVD) were investigated. Argon was used as working gas. Influence of O2 used as oxidizer
was evaluated for determination of hydrophilicity of the films. Surface morphology of the thin TiO2 films deposited on
glass substrates was studied by the atomic force microscopy (AFM) and water contact angle (CA) measurement.
CA tests proved wettability improvement in experiments with oxygen addition.
PACS: 52.77.-j
1. INTRODUCTION
Titanium dioxide TiO2 thin films are used in a variety
of applications because of their outstanding physical and
chemical properties and low cost. In particular, the high
refractive index of the TiO2 (2.75 at 550 nm) and its
excellent transparency in the visible and near-IR spectral
regions make it very appropriate as antireflection coating
and waveguides. There is also growing interest in TiO2
thin films due to their potential applications in
electrochromic display devices [1, 2], gas sensors [3] and
photovoltaics [4].
TiO2 thin films can be prepared by different methods
such as hydrothermal techniques [5], molecular beam
epitaxy [6], sputtering [7], sol-gel [8], chemical vapour
deposition [9, 10] and others. Among these, plasma
enhanced chemical vapour deposition (PE-CVD) at the
atmospheric pressure is a new sample of cheap way to
prepare various thin films. This method offers important
advantages such as: avoidance of wet and hazardous
chemical processes, enhancement of chemical reactions,
larger plasma volume, availability for in-line continuous
deposition process without necessity of pumping. A new
method of thin film deposition by low temperature plasma
at atmospheric pressure might be ideally suited for
deposition of inorganic and organo-inorganic thin films
on different types of substrate, including thermal sensitive
polymer substrates.
This paper presents results of study of TiO2 thin films
deposited on glass substrate by ADBD PE-CVD process
(preliminary results were partially represented in [11]).
We studied the influence of temperature of the precursor
evaporation and gas flow rates on TiO2 thin film
formation and the quality of the TiO2 film.
2. EXPERIMENTAL
The experiments were carried out in a plexiglass
reactor (90x79x41) mm. ADBD CVD system consists of
reactor, gas input and AC power supply as schematically
shown in Fig. 1. Two parallel brass electrodes with
discharge gap of 4 mm were placed into the plasma
reactor. Films were deposited on the glass substrates.
During deposition ADBD power was about 350 mW
(ADBD supply voltage (12.5−14) kV/50 Hz). The
dimensions of the HV and ground electrodes were
(40x17x18) mm and (45x8x18) mm, respectively. HV
electrode was covered by the glass plate ((70x46x1) mm).
The deposition time (t) for all samples was 10 min.
Thin films deposition was performed at atmospheric
pressure. Titanium tetraisopropoxide (TTIP) (97%) was
used as metalorganic precursor and Ar as the carrier gas.
Argon flow rate (QAr) was 0.5 and 1 l/min, respectively.
Experiments were carried out with oxidizer O2 (flow rates
(QO2) 3.0 and 5.0 l/min, respectively) and in the air
without oxygen addition. Argon and oxygen were mixed
in the ground electrode cavity and the mixture flew
through the hole in the electrode (diameter 3 mm) into the
discharge gap. The gas stream was monitored using mass
flow meters. Experiments were performed with 20˚C,
30˚C and 40˚C temperature (T) of TTIP in the bubbler.
Amount of TTIP in the mixture was governed by change
of evaporator temperature and the Ar flow rate through
the evaporator.
Experiments were performed in air (relative humidity
of 35–40% and room temperature 20−22˚C). For contact
angle measurements distilled water was used as the test
liquid. Water drop size was kept constant (at ~0.5 μl). A
drop of water was gently placed on the experimental
surface, and a photograph of the side profile of the liquid
drop was taken using a camera. The base of the liquid
drop was held in the same horizontal plane as the camera
lens. The images were taken in 60 s after release of the
water drop.
Fig.1. Scheme of the apparatus: 1 – HV electrode,
2 – dielectric barrier, 3 – substrate, 4 – ground electrode,
5 – evaporator, 6 – mass flow controller, 7 – HV supply
PROBLEMS OF ATOMIC SCIENCE AND TECHNOLOGY. 2008. № 6. 177
Series: Plasma Physics (14), p. 177-179.
The values of the contact angles, shown in this paper,
were obtained using Young curve fitting based on the
imaged sessile water drop profile (average of
measurements over an extended area of deposited
samples).
3. RESULTS AND DISCUSSION
The morphology analysis of all samples was
performed by atomic force microscopy (AFM) (for
examples see Figs. 2). Fig. 2a shows the uniform and
homogeneous surface with few sharp small tips; it
indicates the needle growth of the films structure due to
the non-homogeneous (streamers) discharge. Doping of
oxygen during deposition process and relatively high
precursor evaporation temperature led to the growth of
some column-like protrusions (Fig. 2b) on the quite
smooth surface. The surface roughness was measured in a
(20×20) μm scan range. Reduction of the TTIP amount by
means of decrease Ar flow rate through evaporator led to
the lowering surface roughness to 10 nm (Fig. 2c).
Increasing oxygen addition to 5.0 l/min resulted in the
needle growth of the films with salient parts and increased
surface roughness (up to 21 nm). Fig. 2d shows that these
films are not fully homogeneous. Many elongated and
pointed crystallites grew faster, the other led to existence
of heterogeneities and to rougher surface. The
inhomogeneous films growth has following explanation:
the streamer’s head hit locally on the substrate, where it
caused higher temperature and activation of the surface in
these areas. It gave rise to higher material growth rates
than at other places on the substrate. The random
distribution of the streamers resulted in irregularities of
thin film growth.
Results of water contact angle measurements are
shown in the Table. The wide range of CA values for
samples with deposition parameters: QAr 0.5 l/min;
TTTIP 20 ˚C can be explained by existence of deposited
film surface-irregularities, small amount of oxygen bonds
on the films surface and high concentration of carbon
[11]. These assumptions were verified by the AFM
results. Addition and oxygen mixing with Ar/TTIP in the
electrode cavity led to the lowest CA values. CA value
was heavily dependent on the oxygen flow rate and
amount of TTIP.
a
b
c
d
Fig.5. Topography of the TiO2 thin films
a) deposited in air without oxygen addition; the scan size
was (10×10) μm; t=1 min; QAr 0.5 l/min; T TTIP 20 ˚C;
b) t=10 min; QAr 1 l/min; QO2 3.0 l/min; T TTIP 40 ˚C; the
scan size was (20×20) μm;
c) t=10 min, QAr 0.5 l/min; QO2 3.0 l/min; T TTIP 40 ˚C; the
scan size was (20×20) μm;
d) t=10 min; QAr 1 l/min; QO2 5.0 l/min; T TTIP 30 ˚C;
the scan size was (20×20) μm
Contact angle values: t – deposition time, Q – gas flow rate, T TTIP – precursor evaporator temperature
Deposition parameters Angle [degree]
t=10 min; QAr 0.5 l/min; T TTIP 20 ˚C 48.5˚ - 98.2
t=10 min; QAr 1 l/min; QO2 3.0 l/min; T TTIP 40 ˚C 29.5
t=10 min; QAr 0.5 l/min; QO2 3.0 l/min; T TTIP 40 ˚C 32.5
t=10 min; QAr 0.5 l/min; QO2 5.0 l/min; T TTIP 30 ˚C 36.3
PROBLEMS OF ATOMIC SCIENCE AND TECHNOLOGY. 2008. № 6. 178
Series: Plasma Physics (14), p. 177-179.
CONCLUSIONS
Titanium dioxide (TiO2) thin films were prepared on
the glass substrate by ADBD CVD deposition method.
Samples were deposited for different ratios of argon and
oxygen flows and various precursor (TTIP) evaporation
temperature (20˚C, 30˚C and 40˚C). For deposition in air
without oxygen addition contact angle values were
observed in the wide range (48.5˚ - 98.2˚), probably due
to low content of oxidiser (O2) in plasma chemical
reactions. Oxygen in plasma has dual role: dissociation of
TTIP molecules and carbon removal from the reactor (this
was confirmed with XPS measurements, see [11]. Mixing
of Ar/TTIP with oxygen led to more hydrophilic film
deposition with CA ~30˚.
ACKNOWLEDGMENTS
This research was supported by the Czech Technical
University in Prague Research Project CTU 0806213.
REFERENCES
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synthesis of nanosized anatase and rutile TiO2 using
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7. Y. Gao, S.A. Chambers. MBE growth and
characterization of epitaxial TiO2 and Nb-doped TiO2
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8. Q. Ye, P.Y. Liu, Z.F. Tang, L. Zhai. Hydrophilic
properties of nano-TiO2 thin films deposited by RF
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9. L.M. Nikolić, L. Radonjić, V.V. Srdić. Effect of
substrate type on nanostructured titania sol–gel
coatings for sensors applications // Ceramics
International. 2005, v. 31, № 2, p. 261-266.
10. D. Byun, Y. Jin et. al. Photocatalytic TiO2 deposition
by chemical vapor deposition // Journal of
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11. C. Jimenez, D.De Barros, A. Darraz et. al. Deposition
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12. Y. Klenko. Atmospheric DBD Plasma Application
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Article received 22.09.08.
НАНЕСЕНИЕ ТОНКИХ ПЛЕНОК TiO2 С ИСПОЛЬЗОВАНИЕМ АТМОСФЕРНОГО
ДИЭЛЕКТРИЧЕСКОГО БАРЬЕРНОГО РАЗРЯДА
Ю. Кленько, Я. Пихал
Было исследовано влияние температуры прекурсора тетраизопропоксида титана, скорости потока
прекурсора и газа на поверхностные свойства пленок диоксида титана, нанесенных в атмосферном
диэлектрическом барьерном разряде методом химического осаждения из газовой фазы. Аргон был использован
как рабочий газ. Также исследовалось влияние кислорода как окислителя на гидрофильность пленок.
Морфология поверхности тонких пленок TiO2, нанесенных на стеклянные подложки, была исследована атомно-
силовой микроскопией и измерением контактного угла. Тестирование методом измерения контактного угла
доказало улучшение гидрофильности пленок в экспериментах, проведенных с дополнительной подачей
кислорода.
НАНЕСЕННЯ ТОНКИХ ПЛIВОК TiO2 З ВИКОРИСТАННЯМ АТМОСФЕРНОГО ДIЕЛЕКТРИЧНОГО
БАР’ЄРНОГО РОЗРЯДУ
Ю. Кленько, Я. Пихал
Було досліджено вплив температури прекурсору тетраізопропоксиду титану, швидкості потоку
прекурсора і газу на поверхневі властивості плівок діоксиду титану, нанесених в атмосферному
діелектричному бар'єрному розряді методом хімічного осадження з газової фази. Аргон був використаний як
робочий газ. Також досліджувався вплив кисню як окислювача на гідрофільність плівок. Морфологія
поверхні тонких плівок, нанесених на скляні підкладки, була досліджена атомно-силовою мікроскопією і
виміром контактного кута. Тестування методом виміру контактного кута довело поліпшення гідрофільності
плівок в експериментах, проведених з додаванням кисню.
Acknowledgments
|
| id | nasplib_isofts_kiev_ua-123456789-110976 |
| institution | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| issn | 1562-6016 |
| language | English |
| last_indexed | 2025-12-01T04:36:23Z |
| publishDate | 2008 |
| publisher | Національний науковий центр «Харківський фізико-технічний інститут» НАН України |
| record_format | dspace |
| spelling | Klenko, Y. Píchal, J. 2017-01-07T15:40:40Z 2017-01-07T15:40:40Z 2008 Deposition of TiO₂ thin films using atmospheric dielectric barrier discharge / Y. Klenko, J. Píchal // Вопросы атомной науки и техники. — 2008. — № 6. — С. 177-179. — Бібліогр.: 12 назв. — англ. 1562-6016 PACS: 52.77.-j https://nasplib.isofts.kiev.ua/handle/123456789/110976 In this paper the influence of precursor (titanium tetraisopropoxide (TTIP)) temperature, precursor and gas flow rates on the surface properties of TiO₂ thin films deposited by atmospheric dielectric barrier discharge (ADBD) chemical vapour deposition (CVD) were investigated. Argon was used as working gas. Influence of O₂ used as oxidizer was evaluated for determination of hydrophilicity of the films. Surface morphology of the thin TiO2 films deposited on glass substrates was studied by the atomic force microscopy (AFM) and water contact angle (CA) measurement. CA tests proved wettability improvement in experiments with oxygen addition. Було досліджено вплив температури прекурсору тетраізопропоксиду титану, швидкості потоку прекурсора і газу на поверхневі властивості плівок діоксиду титану, нанесених в атмосферному діелектричному бар'єрному розряді методом хімічного осадження з газової фази. Аргон був використаний як робочий газ. Також досліджувався вплив кисню як окислювача на гідрофільність плівок. Морфологія поверхні тонких плівок, нанесених на скляні підкладки, була досліджена атомно-силовою мікроскопією і виміром контактного кута. Тестування методом виміру контактного кута довело поліпшення гідрофільності плівок в експериментах, проведених з додаванням кисню. Было исследовано влияние температуры прекурсора тетраизопропоксида титана, скорости потока прекурсора и газа на поверхностные свойства пленок диоксида титана, нанесенных в атмосферном диэлектрическом барьерном разряде методом химического осаждения из газовой фазы. Аргон был использован как рабочий газ. Также исследовалось влияние кислорода как окислителя на гидрофильность пленок. Морфология поверхности тонких пленок TiO₂, нанесенных на стеклянные подложки, была исследована атомно-силовой микроскопией и измерением контактного угла. Тестирование методом измерения контактного угла доказало улучшение гидрофильности пленок в экспериментах, проведенных с дополнительной подачей кислорода. This research was supported by the Czech Technical University in Prague Research Project CTU 0806213. en Національний науковий центр «Харківський фізико-технічний інститут» НАН України Вопросы атомной науки и техники Low temperature plasma and plasma technologies Deposition of TiO₂ thin films using atmospheric dielectric barrier discharge Нанесення тонких плiвок TiO₂ з використанням атмосферного дiелектричного бар’єрного розряду Нанесение тонких пленок TiO₂ с использованием атмосферного диэлектрического барьерного разряда Article published earlier |
| spellingShingle | Deposition of TiO₂ thin films using atmospheric dielectric barrier discharge Klenko, Y. Píchal, J. Low temperature plasma and plasma technologies |
| title | Deposition of TiO₂ thin films using atmospheric dielectric barrier discharge |
| title_alt | Нанесення тонких плiвок TiO₂ з використанням атмосферного дiелектричного бар’єрного розряду Нанесение тонких пленок TiO₂ с использованием атмосферного диэлектрического барьерного разряда |
| title_full | Deposition of TiO₂ thin films using atmospheric dielectric barrier discharge |
| title_fullStr | Deposition of TiO₂ thin films using atmospheric dielectric barrier discharge |
| title_full_unstemmed | Deposition of TiO₂ thin films using atmospheric dielectric barrier discharge |
| title_short | Deposition of TiO₂ thin films using atmospheric dielectric barrier discharge |
| title_sort | deposition of tio₂ thin films using atmospheric dielectric barrier discharge |
| topic | Low temperature plasma and plasma technologies |
| topic_facet | Low temperature plasma and plasma technologies |
| url | https://nasplib.isofts.kiev.ua/handle/123456789/110976 |
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