Synthesis of TiO₂ different phase by DC magnetron sputtering
The enhanced interest to synthesis of thin and extra-thin films using for surface materials modification continue to be quite actual up to now. A special attention is drawn to coatings having important for practical applications characteristics with costs-effective production. These may be the films...
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Національний науковий центр «Харківський фізико-технічний інститут» НАН України
2014
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| Цитувати: | Synthesis of TiO₂ different phase by DC magnetron sputtering / A. Dobrovolskiy, A. Goncharov, E. Kostin, E. Frolova // Вопросы атомной науки и техники. — 2014. — № 6. — С. 145-148. — Бібліогр.: 18 назв. — англ. |
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irk-123456789-819482015-06-03T20:51:23Z Synthesis of TiO₂ different phase by DC magnetron sputtering Dobrovolskiy, A. Goncharov, A. Kostin, E. Frolova, E. Низкотемпературная плазма и плазменные технологии The enhanced interest to synthesis of thin and extra-thin films using for surface materials modification continue to be quite actual up to now. A special attention is drawn to coatings having important for practical applications characteristics with costs-effective production. These may be the films of binary compounds of certain metals, particularly, titanium nitride and titanium oxide. The last compound possesses the utmost significance due to wide range of its unique physical, chemical and biological properties. Functional coatings of titanium dioxide synthesis with nanoscale thickness is of considerable interest since it allows essential economy of the material and the increase of manufacturing productivity with the decrease of production cost. To create a scientific basis of nanotechnologies researchers explore different coatings methods, including the ion-plasma methods. Among them, reactive magnetron sputtering seems to be promising: DC magnetron coating allows to deposit titania in amorphous and crystal phase and control results by variation of deposition conditions. The substrate material influences coating phase, as well as discharge characteristics. The thermal linear expansion coefficient does not influence line blue shift in Raman spectra of deposited films in our experiments. The influence of film annealing after deposition up to 800ºC on dioxide crystalline phase of the film is shown. В настоящее время продолжает сохраняться значительный интерес к созданию тонких и сверхтонких пленок, модифицирующих поверхностные свойства материалов. Особое внимание уделяется покрытиям, имеющим важные для практического применения характеристики при невысокой себестоимости процесса их синтеза. К таким можно отнести пленки бинарных соединений некоторых химически активных металлов, например, нитридов и оксидов титана. Последние имеют особое значение в силу широкого спектра уникальных физико-химических и биологических характеристик. Отдельный интерес представляет получение функциональных пленок диоксида титана наноразмерной толщины, что позволяет существенно экономить материал и ускорять осаждение покрытий при снижении их себестоимости. В процессе создания научных основ современных нанотехнологий используются различные методы осаждения покрытий, в том числе и ионно-плазменные. Среди них перспективными являются методы реактивного магнетронного осаждения. Осаждение в DC-магнетроне позволяет синтезировать покрытия из диоксида титана в аморфной и кристаллической фазах в зависимости от условий осаждения. Материал подложки оказывает влияние на возможность получения рутила наряду с условиями осаждения. Изменение в широких пределах линейного коэффициента термического расширения подложки не оказывает существенного влияния на сдвиг линий рамановского спектра пленок анатаза. Показано влияние отжига в воздухе до 800ºС после осаждения на полиморфную модификацию диоксида титана в пленках. Останнім часом зберігається підвищена увага до створення тонких та надтонких плівок, що змінюють по¬верхневі властивості матеріалів. Особлива увага приділяється покриттям, що демонструють характеристики, важливі для практичного застосування. До таких можна віднести плівки бінарних сполук деяких хімічно активних металів, наприклад, нітридів та оксидів титану. Останні мають особливе значення через широкий спектр їх унікальних фізико-хімічних та біологічних характеристик. Окрему зацікавленість викликає одержання функціональних плівок двоокису титану нанорозмірної товщини. Це дозволяє суттєво економити матеріал та пришвидшити осадження покриттів з одночасним зменшенням їх собівартості. У процесі створення наукових основ сучасних нанотехнологій використовуються різні методи осадження покриттів, зокрема й іонно-плазмові. Серед них перспективними є методи реактивного магнетронного осаджен¬ня. Осадження в DC-магнетроні дозволяє синтезувати покриття з двоокису титану в аморфній або кристалічній фазах у залежності від умов осадження. Матеріал підкладки впливає на можливість утворення з рутилу на рівні з умовами осадження. Зміни в широкому діапазоні лінійного коефіцієнта термічного розширення суттєво не впливають на зсув ліній раманівського спектра плівок анатазу. Показано також вплив відпалювання в повітрі до 800ºС після осадження на поліморфну модифікацію двоокису титану в плівках. 2014 Article Synthesis of TiO₂ different phase by DC magnetron sputtering / A. Dobrovolskiy, A. Goncharov, E. Kostin, E. Frolova // Вопросы атомной науки и техники. — 2014. — № 6. — С. 145-148. — Бібліогр.: 18 назв. — англ. 1562-6016 PACS: 81.15.-z, 52.77.Dq; 81.10.Pq, 68.55.-a http://dspace.nbuv.gov.ua/handle/123456789/81948 en Вопросы атомной науки и техники Національний науковий центр «Харківський фізико-технічний інститут» НАН України |
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Digital Library of Periodicals of National Academy of Sciences of Ukraine |
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| topic |
Низкотемпературная плазма и плазменные технологии Низкотемпературная плазма и плазменные технологии |
| spellingShingle |
Низкотемпературная плазма и плазменные технологии Низкотемпературная плазма и плазменные технологии Dobrovolskiy, A. Goncharov, A. Kostin, E. Frolova, E. Synthesis of TiO₂ different phase by DC magnetron sputtering Вопросы атомной науки и техники |
| description |
The enhanced interest to synthesis of thin and extra-thin films using for surface materials modification continue to be quite actual up to now. A special attention is drawn to coatings having important for practical applications characteristics with costs-effective production. These may be the films of binary compounds of certain metals, particularly, titanium nitride and titanium oxide. The last compound possesses the utmost significance due to wide range of its unique physical, chemical and biological properties. Functional coatings of titanium dioxide synthesis with nanoscale thickness is of considerable interest since it allows essential economy of the material and the increase of manufacturing productivity with the decrease of production cost. To create a scientific basis of nanotechnologies researchers explore different coatings methods, including the ion-plasma methods. Among them, reactive magnetron sputtering seems to be promising: DC magnetron coating allows to deposit titania in amorphous and crystal phase and control results by variation of deposition conditions. The substrate material influences coating phase, as well as discharge characteristics. The thermal linear expansion coefficient does not influence line blue shift in Raman spectra of deposited films in our experiments. The influence of film annealing after deposition up to 800ºC on dioxide crystalline phase of the film is shown. |
| format |
Article |
| author |
Dobrovolskiy, A. Goncharov, A. Kostin, E. Frolova, E. |
| author_facet |
Dobrovolskiy, A. Goncharov, A. Kostin, E. Frolova, E. |
| author_sort |
Dobrovolskiy, A. |
| title |
Synthesis of TiO₂ different phase by DC magnetron sputtering |
| title_short |
Synthesis of TiO₂ different phase by DC magnetron sputtering |
| title_full |
Synthesis of TiO₂ different phase by DC magnetron sputtering |
| title_fullStr |
Synthesis of TiO₂ different phase by DC magnetron sputtering |
| title_full_unstemmed |
Synthesis of TiO₂ different phase by DC magnetron sputtering |
| title_sort |
synthesis of tio₂ different phase by dc magnetron sputtering |
| publisher |
Національний науковий центр «Харківський фізико-технічний інститут» НАН України |
| publishDate |
2014 |
| topic_facet |
Низкотемпературная плазма и плазменные технологии |
| url |
http://dspace.nbuv.gov.ua/handle/123456789/81948 |
| citation_txt |
Synthesis of TiO₂ different phase by DC magnetron sputtering / A. Dobrovolskiy, A. Goncharov, E. Kostin, E. Frolova // Вопросы атомной науки и техники. — 2014. — № 6. — С. 145-148. — Бібліогр.: 18 назв. — англ. |
| series |
Вопросы атомной науки и техники |
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2025-07-06T07:43:55Z |
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2025-07-06T07:43:55Z |
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| fulltext |
ISSN 1562-6016. ВАНТ. 2014. №6(94)
PROBLEMS OF ATOMIC SCIENCE AND TECHNOLOGY. 2014, №6. Series: Plasma Physics (20), p. 145-148. 145
SYNTHESIS OF TiO2 DIFFERENT PHASE BY DC MAGNETRON
SPUTTERING
A. Dobrovolskiy
1
, A. Goncharov
1
, E. Kostin
2
, E. Frolova
1
1
Institute of Physics NAS of Ukraine, Kiev, Ukraine;
2
Institute for Nuclear Research NASU, Kiev, Ukraine
E-mail: dobr@iop.kiev.ua
The enhanced interest to synthesis of thin and extra-thin films using for surface materials modification continue
to be quite actual up to now. A special attention is drawn to coatings having important for practical applications
characteristics with costs-effective production. These may be the films of binary compounds of certain metals,
particularly, titanium nitride and titanium oxide. The last compound possesses the utmost significance due to wide
range of its unique physical, chemical and biological properties. Functional coatings of titanium dioxide synthesis
with nanoscale thickness is of considerable interest since it allows essential economy of the material and the
increase of manufacturing productivity with the decrease of production cost. To create a scientific basis of
nanotechnologies researchers explore different coatings methods, including the ion-plasma methods. Among them,
reactive magnetron sputtering seems to be promising: DC magnetron coating allows to deposit titania in amorphous
and crystal phase and control results by variation of deposition conditions. The substrate material influences coating
phase, as well as discharge characteristics. The thermal linear expansion coefficient does not influence line blue shift
in Raman spectra of deposited films in our experiments. The influence of film annealing after deposition up to
800ºC on dioxide crystalline phase of the film is shown.
PACS: 81.15.-z, 52.77.Dq; 81.10.Pq, 68.55.-a
INTRODUCTION
To create a scientific basis for modern nanotechnolo-
gies, researchers study various coatings deposition
methods, including the ion-plasma methods. Among
them, reactive magnetron sputtering seems to be promi-
sing: it uses only a metallic target and a reactive gas
(N2, O2) as an addition to a plasma forming gas (Ar) to
synthesize coatings. Absence of toxic chemical
solutions and gaseous reagents makes this method
maximally friendly to environment and does not require
creation of deactivating facilities for recycling a waist of
chemical reactions. We present the synthesis deposition
method of TiO2 nano- films in different phase by DC
inverted cylindrical magnetron and influence of
deposition process parameters on the result. Earlier we
have shown existence of peculiarities in behavior of
intensities of spectrum lines of the magnetron discharge
plasma emission in presence of substances participating
in the synthesis of TiO2 nano-films [1, 2]. Existence of
correlation between emission spectra peculiarities and
electrophysical discharge parameters enables reliable
control of operating point of titanium dioxide deposition
in cylindrical magnetron, and ensures synthesis
stoichiometric titanium dioxide films. It was noted [1]
that at cold substrate one can obtain only amorphous
titanium dioxide film in our range of the deposition
parameters. At the same time, heating the substrate
above 350ºC causes reliable anatase synthesis.
Variations of the gas discharge parameters and the
substrate temperature enable obtaining anatase films of
different density, photocatalytic activity and with
different crystal size [2-4].
Necessity of the substrate temperature rise above
400
о
C does not enable use of borosilicate glasses for the
synthesis of rutile films. Due to that, we used substrates
made of high temperature materials for making possible
their heating up to higher temperature values. Fused
silica substrate served as a test one for comparison with
earlier obtained results.
1. SETUP AND METHODS
Setup in details is described in [5, 6]. The original
DC inverted cylindrical magnetron is described in [7].
Films deposition was controlled with a Plazma Spec
optical spectrometer, which is based on charge-coupled
devices and has a resolution of 0.6 nm in the
wavelength range λ=350…820 nm. The optical
spectrum recording time was 5 ms, and we were able to
record an entire spectrum and its selected lines [8].
The Raman spectra of the films were recorded in
the backscattering geometry at room temperature. To
excite vibrations, we used line 785.0 nm of an
RANISHAW In Via Raman Microscope. The
surface morphology and the roughness of the films we
explored with a NanoScope IIIa Dimension 3000 atomic
force microscope (AFM). The thickness and the
refractive index of the films were measured by
ellipsometry on an LEF3M1 ellipsometer at λ =
632.8 nm [1-4], and by method of [9] using optical
transmission.
2. RESULTS AND DISCUSSIONS
To define the suitable conditions to synthesis of
rutile films the experiments with heated substrates were
carried out. For the results to be considered, the
substrate was heated up to 560°C. At that, different
results were obtained on different substrates. Fig. 1
represents Raman spectrum of the film deposited onto a
fused silica.
The spectrum is separated from the substrate lines.
Frequency positions of the lines in the spectrum
correspond to 158.2 cm
-1
, 413.2 cm
-1
, 513 cm
-1
,
645.7 cm
–1
. Taking into account blue shift of the lines
for nano-crystal anatase samples, it agrees with the data
of Ohsaka et al. [10] for anatase: Eg(1) 144 cm
–1
,
146 ISSN 1562-6016. ВАНТ. 2014. №6(94)
Eg(2)197 cm
–1
, B1g 399 cm
-1
, (A1g +B1g) 514 cm
–1
,
Eg(3) 639 cm
–1
. The last enables identification of the
film on fused silica substrate as one composed of
anatase phase with the lines having blue shift. All the
lines, with an exception of [A1g +B1g(2)], possess
essential blue shift, which is inherent to a very fine-grain
samples [11]. Half-width of G lines Eg(1) comprises
31.2 cm
–1
, which is essentially more than the half-width
G=8.6 cm
−1
for rough-grain anatase powder [12].
Fig. 1. Raman spectrum of the TіO2 film deposited on a
fused silica substrate at temperature of 560 °C and
argon pressure of 3•10
–3
Torr after separating the
substrate spectrum. Above the spectrum lines, their
frequency positions are shown on a basis of the results
of the lines approximation by Lorentzian function
The result for the film on corundum is shown in
Fig. 2. The lines 378.7 cm
−1
(Eg), 427.2 cm
−1
(Eg),
643.6 cm
−1
(A1g) belong to corundum substrate. In the
film spectrum one can clearly see the line 157.9 cm
-1
,
which, taking the blue shift into account, may be
considered as line Eg(1) 144 cm
–1
of solid polycrystalline
anatase. The other lines, which were determined for the
film on fused silica as B1g 413.2 cm
-1
, (A1g +B1g)
513 cm
-1
, Eg(3) 645.7 cm
-1
in case of corundum are
masked by the bases of the substrate lines.
It is illustrated by comparison with the film spectrum
on fused silica shown in Fig. 2 as dotted line. Position
ω=157.9 cm
-1
of line Eg(1) and its half-width
G=29.1 cm
−1
for anatase film on corundum are close to
the position and the half-width for the film on fused
silica (ω=158.2 cm
-1
, G=31.2 cm
-1
).
Fig. 3 presents the spectrum for the film on fluorite.
Line at 320 cm
–1
belongs to fluorite.
Frequency positions of the lines in the spectrum of
TiO2 film on CaF2 substrate are, as follows: 160.2 cm
–1
,
238.7 cm
–1
, 377.5 cm
–1
, 473.0 cm
–1
, 592.3 cm
–1
.
Taking into account possible shifts of the lines in
nano-crystal anatase and rutile samples, these may
correspond to the following lines: 159 cm
–1
– anatase
line Eg (1) 144 cm
–1
with blue shift, 238.7 cm
–1
– rutile
line 235 cm
-1
(two-phonon process), 377.5 cm
–1
and
473.0 cm
–1
– are not defined, 592.3 cm
–1
– rutile line
A1g 612 cm
–1
with red shift.
It is known from published data [13] that in rutile
with crystallite dimensions less than 25 nm, lines Eg
(447 cm
–1
) and A1g (612 cm
–1
) exhibit red shift with
decrease of the dimensions. Besides, the lines are
broadened, and their intensity decreases. In [14] also
were determined red shift of rutile line A1g (612 cm
–1
)
and blue shift of rutile line 235 cm
-1
with the decrease of
crystal dimensions. On a basis of all said above, on can
consider the film as one of rutile and anatase mixture.
At that, blue shift of line Eg(1) 159 cm
–1
is practically
analogous (a bit more) to those for the films on
corundum (up to 157.9 cm
−1
) and on fused silica (up to
158.2 cm
−1
).
Fig. 2. Raman spectrum of the TіO2 film deposited on a
corundum substrate at temperature 560°C and argon
pressure 3•10
–3
Torr. Frequency positions are shown
above the lines. The dotted line shows the spectrum of
TіO2 film from Fig. 1 deposited on the fused silica
substrate under the same conditions
Fig. 3. Raman spectrum of the TіO2 film deposited on a
CaF2 substrate at temperature 560°C and argon
pressure of 3•10
–3
Torr. Spectral lines were fitted by a
Lorentzian function. Above the lines, their frequency
positions are shown
It should be notes that for Al2O3 (corundum), thermal
linear expansion coefficient (TLEC) at 300 K equals
5,6 х 10
-6
/K parallel and 5 x 10
-6
/K perpendicular to
optical axis, which is close to anatase TLEC
(4,47×10
−6
/K parallel to a axis and 8,43×10
−6
/K parallel
to c axis [15]). For SiO2 (fused silica) TLEC at 300 K
comprises 0.55×10
-6
/C [16], which is almost an order of
magnitude less than that for anatase. It means that
anatase films deposited onto fused silica at higher
substrate temperature, and after that cooled down to
room temperature, are in stretched state. For CaF2
(fluorite) TLEC comprises 18.9 ×10
-6
/K at 300 K [17],
which is 3 to 4 times more than that for anatase. Thus,
anatase films after deposition onto heated fluorite, and
ISSN 1562-6016. ВАНТ. 2014. №6(94) 147
subsequent cooling down to room temperature, are in
compressed state.
For rutile film on three chosen substrate types, the
same tendencies for tensions in the films take place since
rutile TLEC at 300 K comprises 7.14 ×10
-6
/K parallel to a
axis and 9.19 ×10
-6
/K parallel to c axis [18].
Thus, difference in thermal linear expansion
coefficients for the substrates has no significant
influence on blue shift value for line Eg(1) in Raman
spectra of anatase films, although average TLEC for
polycrystalline anatase (5.79×10
−6
/K) is almost an order
of magnitude more than that for fused silica, and 3 to 4
times less than that for fluorite.
After annealing of the films in air subsequently for 3
hours at 700
о
C temperature and for 3 hours at 800
о
C,
Raman spectra for the films on fused silica and corundum
did not show presence of rutile. Blue shift of the lines
decreased, which is considered by us as a consequence of
grain dimensions growth after the annealing. Intensity of
the lines increased, which can be attributed to improvement
of the substance order due to annealing of the defects and
decrease of contribution of grain boundaries.
For the film on CaF2 substrate another situation
occurs (Fig. 4). Changes in Raman spectrum are
observed after the annealing. Frequency positions of the
lines now are: 154 cm
–1
, 238 cm
–1
, 321 cm
–1
, 395 cm
-1
,
520 cm
–1
, 649 cm
–1
, which, taking the shifts into
account, may correspond to: 154 cm
–1
– anatase line
Eg(1) 144 cm
–1
with blue shift, 238 cm
–1
– rutile line
235 cm
–1
, 395 cm
-1
– anatase line 399 cm
–1
B1g,
649 cm
–1
– anatase line Eg. (3) 639 cm
–1
with blue shift.
Line at 321 cm
–1
belongs to fluorite.
Thus, we again have the film with anatase and rutile
mixture. At the same time, for anatase line Eg. (1) the
blue shift decreased from 160.2 to 154 cm
–1
), the
intensity increased, and the half-width decreased.
Anatase line 649 cm
–1
is clearly visible. Observed
changes can be due to growth of the crystallites and
annealing of the defects.
Fig. 4. Raman spectrum of the TіO2 film deposited on a
CaF2 substrate at temperature of 560°C, under an argon
pressure of 3•10
–3
Torr, and then annealed in air at
700 C for a 3 hours. Above the spectrum lines, their fre-
quency positions by results of approximation are shown
Rutile appearance at annealing of the samples only
on CaF2 can be due to both appropriate influence of the
substrate material, and presence of contraction tension
in the film due to different TLEC values for the
substrate and the film. As it is known, rutile is titanium
dioxide modification with higher density.
We study the surface states of the deposited samples
with atomic force microscope (AFM). The results are
presented in Table. Ra value are calculated with
exponent q = 1 and absolute values of the data (zero
mean), as for the Rms this exponent is q = 2. S is the
area of scan window, Sп – the area of film surface.
Statistic data on surface characteristics of the test films
Substrate type
Ra,
nm
Rms,
Nm
Sп/S
Fused silica 3.6 4.55 1.4
Corundum 5 6.4 1.6
Fluorite 10 13.5 1.7
One can see from the table that the maximum
roughness is observed for the films on fluorite. High
substrate temperature at deposition of the films
promotes formation of larger grains and developed
surface [2]. In general, usual stochastic relief is formed
without specific peculiarities.
CONCLUSIONS
Presented results enable to conclude that the substrate
material influences the formation of particular polymorphic
modification of titanium dioxide at magnetron-based
deposition of the films. Chemical elements contained in the
film can shift boundary temperature of anatase-to-rutile
transition. TLEC of the substrate in a wide range does not
have essential effect on the shift of anatase Raman spectrum
lines. The shift and the half-width of the lines can be used for
an estimation of crystallite dimensions, similarly to that in
case of powders. Synthesis of amorphous titanium dioxide
and its polymorphic modifications anatase and rutile are
possible in direct current magnetron at proper choice of the
substrate material and the synthesis conditions.
This work is supported in part by Grant № 86/14-H
of Presidium of NAS of Ukraine.
REFERENCES
1. A.A. Goncharov, A.N. Dobrovolskiy, et al. Optical,
structural and photocatalythic features of nano-sized films
of titanium dioxide deposited in magnetron discharge
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Article received 21.10.2014.
СИНТЕЗ РАЗЛИЧНЫХ ФАЗ TiO2 В DC-МАГНЕТРОНЕ
A. Добровольский, A. Гончаров, E. Костин, E. Фролова
В настоящее время продолжает сохраняться значительный интерес к созданию тонких и сверхтонких
пленок, модифицирующих поверхностные свойства материалов. Особое внимание уделяется покрытиям,
имеющим важные для практического применения характеристики при невысокой себестоимости процесса
их синтеза. К таким можно отнести пленки бинарных соединений некоторых химически активных металлов,
например, нитридов и оксидов титана. Последние имеют особое значение в силу широкого спектра
уникальных физико-химических и биологических характеристик. Отдельный интерес представляет
получение функциональных пленок диоксида титана наноразмерной толщины, что позволяет существенно
экономить материал и ускорять осаждение покрытий при снижении их себестоимости. В процессе создания
научных основ современных нанотехнологий используются различные методы осаждения покрытий, в том
числе и ионно-плазменные. Среди них перспективными являются методы реактивного магнетронного
осаждения. Осаждение в DC-магнетроне позволяет синтезировать покрытия из диоксида титана в аморфной
и кристаллической фазах в зависимости от условий осаждения. Материал подложки оказывает влияние на
возможность получения рутила наряду с условиями осаждения. Изменение в широких пределах линейного
коэффициента термического расширения подложки не оказывает существенного влияния на сдвиг линий
рамановского спектра пленок анатаза. Показано влияние отжига в воздухе до 800ºС после осаждения на
полиморфную модификацию диоксида титана в пленках.
СИНТЕЗ РІЗНИХ ФАЗ TiO2 У DC-МАГНЕТРОНІ
A. Добровольський, О. Гончаров, Є. Костін, О. Фролова
Останнім часом зберігається підвищена увага до створення тонких та надтонких плівок, що змінюють по-
верхневі властивості матеріалів. Особлива увага приділяється покриттям, що демонструють характеристики,
важливі для практичного застосування. До таких можна віднести плівки бінарних сполук деяких хімічно
активних металів, наприклад, нітридів та оксидів титану. Останні мають особливе значення через широкий
спектр їх унікальних фізико-хімічних та біологічних характеристик. Окрему зацікавленість викликає
одержання функціональних плівок двоокису титану нанорозмірної товщини. Це дозволяє суттєво економити
матеріал та пришвидшити осадження покриттів з одночасним зменшенням їх собівартості. У процесі
створення наукових основ сучасних нанотехнологій використовуються різні методи осадження покриттів,
зокрема й іонно-плазмові. Серед них перспективними є методи реактивного магнетронного осадження.
Осадження в DC-магнетроні дозволяє синтезувати покриття з двоокису титану в аморфній або кристалічній
фазах у залежності від умов осадження. Матеріал підкладки впливає на можливість утворення з рутилу на
рівні з умовами осадження. Зміни в широкому діапазоні лінійного коефіцієнта термічного розширення
суттєво не впливають на зсув ліній раманівського спектра плівок анатазу. Показано також вплив
відпалювання в повітрі до 800ºС після осадження на поліморфну модифікацію двоокису титану в плівках.
http://www.sciencedirect.com/science/journal/09242031
http://www.sciencedirect.com/science/journal/09242031
http://www.mt-berlin.com/frames_cryst/crystals_frameset1.htm
http://www.mt-berlin.com/frames_cryst/crystals_frameset1.htm
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