Elemental and phase analysis of nanocomposite coatings on basis Ti-Hf-Si-N system received by the vacuum-arc deposition method
Coatings on the basis Ti-Hf-Si-N system were synthesized by vacuum-arc deposition method from the uniflow and separated ion-plasma flow. The morphology, elemental and phase composition of coatings were investigated. The dependence of the characteristics of the coating from the physical and tec...
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Науковий фізико-технологічний центр МОН та НАН України
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| Цитувати: | Elemental and phase analysis of nanocomposite coatings on basis Ti-Hf-Si-N system received by the vacuum-arc deposition method / V.V. Grudnitskiy, V.M. Beresnev, А.А. Drobyshevskaya, P.V. Turbin, I.N. Toryanik, S.S. Grankin, D.А. Kolesnikov, U.S. Nemchenko // Физическая инженерия поверхности. — 2012. — Т. 10, № 3. — С. 286–294. — Бібліогр.: 14 назв. — англ. |
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Grudnitskiy, V.V. Beresnev, V.M. Drobyshevskaya, А.А. Turbin, P.V. Toryanik, I.N. Grankin, S.S. Kolesnikov, D.А. Nemchenko, U.S. 2016-04-19T18:13:54Z 2016-04-19T18:13:54Z 2012 Elemental and phase analysis of nanocomposite coatings on basis Ti-Hf-Si-N system received by the vacuum-arc deposition method / V.V. Grudnitskiy, V.M. Beresnev, А.А. Drobyshevskaya, P.V. Turbin, I.N. Toryanik, S.S. Grankin, D.А. Kolesnikov, U.S. Nemchenko // Физическая инженерия поверхности. — 2012. — Т. 10, № 3. — С. 286–294. — Бібліогр.: 14 назв. — англ. 1999-8074 https://nasplib.isofts.kiev.ua/handle/123456789/98973 621.793: 539.61: 669.018: 620.1 Coatings on the basis Ti-Hf-Si-N system were synthesized by vacuum-arc deposition method from the uniflow and separated ion-plasma flow. The morphology, elemental and phase composition of coatings were investigated. The dependence of the characteristics of the coating from the physical and technological parameters of deposition was installed. The two-phase structure of the coating: a substitutional solution (Ti, Hf)N and quasiamorphous silikonitrid α-Si₃N₄ was determined. The factors that determine the compressive stresses in the coatings were considered. Методом вакуумно-дугового осаждения из прямоточного и сепарированного ионно-плазменного потока синтезированы покрытия на основе системы Ti-Hf-Si-N. Исследована морфология, определен элементный и фазовый состав покрытий. Установлена зависимость характеристик покрытий от физико-технологических параметров осаждения. Определена двухфазная структура покрытия: твердый раствор замещения (Ti, Hf)N и квазиаморфный силиконитрид α-Si₃N₄. Рассмотрены факторы, определяющие сжимающие напряжения в покрытиях. Методом вакуумно-дугового осадження з прямоточного і сепарованого іонно-плазмового потоку синтезовані покриття на основі системи Ti-Hf-Si-N. Досліджено морфологію, визначено елементний і фазовий склад покриттів. Встановлено залежність характеристик покриттів від фізико-технологічних параметрів осадження. Визначена двофазна структура покриття: твердий розчин заміщення (Ti, Hf) N і квазіаморфний силіконітрид α-Si₃N₄. Розглянуто чинники, що визначають стискаючі напруження у покриттях. en Науковий фізико-технологічний центр МОН та НАН України Физическая инженерия поверхности Elemental and phase analysis of nanocomposite coatings on basis Ti-Hf-Si-N system received by the vacuum-arc deposition method Article published earlier |
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Digital Library of Periodicals of National Academy of Sciences of Ukraine |
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DSpace DC |
| title |
Elemental and phase analysis of nanocomposite coatings on basis Ti-Hf-Si-N system received by the vacuum-arc deposition method |
| spellingShingle |
Elemental and phase analysis of nanocomposite coatings on basis Ti-Hf-Si-N system received by the vacuum-arc deposition method Grudnitskiy, V.V. Beresnev, V.M. Drobyshevskaya, А.А. Turbin, P.V. Toryanik, I.N. Grankin, S.S. Kolesnikov, D.А. Nemchenko, U.S. |
| title_short |
Elemental and phase analysis of nanocomposite coatings on basis Ti-Hf-Si-N system received by the vacuum-arc deposition method |
| title_full |
Elemental and phase analysis of nanocomposite coatings on basis Ti-Hf-Si-N system received by the vacuum-arc deposition method |
| title_fullStr |
Elemental and phase analysis of nanocomposite coatings on basis Ti-Hf-Si-N system received by the vacuum-arc deposition method |
| title_full_unstemmed |
Elemental and phase analysis of nanocomposite coatings on basis Ti-Hf-Si-N system received by the vacuum-arc deposition method |
| title_sort |
elemental and phase analysis of nanocomposite coatings on basis ti-hf-si-n system received by the vacuum-arc deposition method |
| author |
Grudnitskiy, V.V. Beresnev, V.M. Drobyshevskaya, А.А. Turbin, P.V. Toryanik, I.N. Grankin, S.S. Kolesnikov, D.А. Nemchenko, U.S. |
| author_facet |
Grudnitskiy, V.V. Beresnev, V.M. Drobyshevskaya, А.А. Turbin, P.V. Toryanik, I.N. Grankin, S.S. Kolesnikov, D.А. Nemchenko, U.S. |
| publishDate |
2012 |
| language |
English |
| container_title |
Физическая инженерия поверхности |
| publisher |
Науковий фізико-технологічний центр МОН та НАН України |
| format |
Article |
| description |
Coatings on the basis Ti-Hf-Si-N system were synthesized by vacuum-arc deposition method from
the uniflow and separated ion-plasma flow. The morphology, elemental and phase composition of
coatings were investigated. The dependence of the characteristics of the coating from the physical
and technological parameters of deposition was installed. The two-phase structure of the coating: a
substitutional solution (Ti, Hf)N and quasiamorphous silikonitrid α-Si₃N₄ was determined. The factors
that determine the compressive stresses in the coatings were considered.
Методом вакуумно-дугового осаждения из прямоточного и сепарированного ионно-плазменного
потока синтезированы покрытия на основе системы Ti-Hf-Si-N. Исследована морфология,
определен элементный и фазовый состав покрытий. Установлена зависимость характеристик покрытий от физико-технологических параметров осаждения. Определена двухфазная структура покрытия: твердый раствор замещения (Ti, Hf)N и квазиаморфный силиконитрид α-Si₃N₄. Рассмотрены факторы, определяющие сжимающие напряжения в покрытиях.
Методом вакуумно-дугового осадження з прямоточного і сепарованого іонно-плазмового потоку синтезовані покриття на основі системи Ti-Hf-Si-N. Досліджено морфологію, визначено елементний і фазовий склад покриттів. Встановлено залежність характеристик покриттів від фізико-технологічних параметрів осадження. Визначена двофазна структура покриття: твердий розчин заміщення (Ti, Hf) N і квазіаморфний силіконітрид α-Si₃N₄. Розглянуто чинники, що визначають стискаючі напруження у покриттях.
|
| issn |
1999-8074 |
| url |
https://nasplib.isofts.kiev.ua/handle/123456789/98973 |
| citation_txt |
Elemental and phase analysis of nanocomposite coatings on basis Ti-Hf-Si-N system received by the vacuum-arc deposition method / V.V. Grudnitskiy, V.M. Beresnev, А.А. Drobyshevskaya, P.V. Turbin, I.N. Toryanik, S.S. Grankin, D.А. Kolesnikov, U.S. Nemchenko // Физическая инженерия поверхности. — 2012. — Т. 10, № 3. — С. 286–294. — Бібліогр.: 14 назв. — англ. |
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286
INTRODUCTION
The development of the new nanostructural coating
with high hardness (> 40 GPa) and thermal stability
(> 1200 °С) is the actual problem of the modern
material science. According to the previous experi-
mental results it can be considered that not only
grains size has strong influence on properties of the
solid but also structural states of interfaces (grains
boundary). As the quantity of atoms at grains bound-
ary reaches about 30 − 50% properties of the ma-
terial are strongly depend on condition of the grains
boundary: gap of the border band (in this band lat-
tice parameter deviate from standard value), disori-
entation of the grains and interfaces, concentration
of the defects at boundary and value of the free vol-
ume.
Nanocrystalline materials that contain nanosized
crystallite along with rather extensive and partially
UDK 621.793: 539.61: 669.018: 620.1
ELEMENTAL AND PHASE ANALYSIS OF NANOCOMPOSITE
COATINGS ON BASIS Ti-Hf-Si-N SYSTEM RECEIVED BY THE VACUUM-ARC
DEPOSITION METHOD
V.V. Grudnitskiy1, V.M. Beresnev1, А.А. Drobyshevskaya2, P.V. Turbin3,
I.N. Toryanik1, S.S. Grankin1, D.А. Kolesnikov4, U.S. Nemchenko1
1V.N. Karazin Kharkiv National University
Ukraine
2National Science Center “Kharkiv Institute of Physics and Technology”
Ukraine
3Scientific Center for Physical Technologies of MESYSU and NASU
Ukraine
4Belgorod State University
Russia
Received 18.09.2012
Coatings on the basis Ti-Hf-Si-N system were synthesized by vacuum-arc deposition method from
the uniflow and separated ion-plasma flow. The morphology, elemental and phase composition of
coatings were investigated. The dependence of the characteristics of the coating from the physical
and technological parameters of deposition was installed. The two-phase structure of the coating: a
substitutional solution (Ti, Hf)N and quasiamorphous silikonitrid α-Si3N4 was determined. The factors
that determine the compressive stresses in the coatings were considered.
Keywords: vacuum-arc deposition method, nanocomposite coatings, nitrides, alloys, superhard, re-
fractory metals.
Методом вакуумно-дугового осаждения из прямоточного и сепарированного ионно-плазменного
потока синтезированы покрытия на основе системы Ti-Hf-Si-N. Исследована морфология,
определен элементный и фазовый состав покрытий. Установлена зависимость характеристик
покрытий от физико-технологических параметров осаждения. Определена двухфазная структура
покрытия: твердый раствор замещения (Ti, Hf)N и квазиаморфный силиконитрид α-Si3N4.
Рассмотрены факторы, определяющие сжимающие напряжения в покрытиях.
Ключевые слова: вакуумно-дуговой метод осаждения, нанокомпозитные покрытия, нитриды,
сплавы, сверхтвердость, тугоплавкие металлы.
Методом вакуумно-дугового осадження з прямоточного і сепарованого іонно-плазмового по-
току синтезовані покриття на основі системи Ti-Hf-Si-N. Досліджено морфологію, визначено
елементний і фазовий склад покриттів. Встановлено залежність характеристик покриттів від
фізико-технологічних параметрів осадження. Визначена двофазна структура покриття: твердий
розчин заміщення (Ti, Hf) N і квазіаморфний силіконітрид α-Si3N4. Розглянуто чинники, що ви-
значають стискаючі напруження у покриттях.
Ключові слова: вакуумно-дуговий метод осадження, надтвердість, нанокомпозитні покриття,
нітриди, сплави, тугоплавкі метали.
V.V. Grudnitskiy, V.M. Beresnev, А.А. Drobyshevskaya, P.V. Turbin, I.N. Toryanik, S.S. Grankin,
D.А. Kolesnikov, U.S. Nemchenko, 2012
287ФІП ФИП PSE, 2012, т. 10, № 3 vol. 10, No. 3
disordered boundaries structure have new proper-
ties by comparison with the large-grained materials.
Obtaining of nanocomposite coatings by ion-
plasma deposition technology requires deposition
on the substrate of multi-component flows. In most
cases the synthesis of coatings is realized by layer-
ing or simultaneous deposition on the substrate in
an atmosphere of reaction gases of flows from two
sources: ion, magnetron, vacuum-arc and a combi-
nation thereof. Such methods of deposition require
the of non-standard equipment. Therefore interest
are the investigations in which nanocomposites re-
ceive on the traditional plants with one cathode
(evaporated target) containing the necessary com-
ponents in the desired ratio. Materials for evapora-
tion receive powder technologies [1, 2] or electron
beam remelting [3]. The paper presents the results
of the development of the new type of Ti-Hf-Si-N-
based superhard nanostructured coatings and anal-
ysis of their elemental composition, the surface mor-
phology and structural-phase state depending on the
physical and technological conditions of their pro-
duction.
ELEMENTAL COMPOSITION AND
SURFACE MORPHOLOGY OF
NANOCOMPOSITE COATINGS BASED Ti,
Hf, Si AND N RECEIVED BY VACUUM-ARC
DEPOSITION METHOD
Coatings on the basis Ti-Hf-Si-N system thickness
of 1.5 mm were formed on the polished surface of
the samples (steel 45) with a diameter of 10 mm
and a height of 3 mm by vacuum-arc deposition
using a pulsed HF voltage by sputtering cathode
Ti+Hf+Si in the molecular nitrogen medium. The
coatings were synthesized from the uniflow ion-plas-
ma flow and with the use of flow separation. A bias
potential was varied in the range –100 V ÷
–200 V and was applied to the substrate from a
HF generator with impulses of damped oscillations
of ≤ 1 MHz frequency.
The elemental composition of coatings obtained
by vacuum-arc deposition was analyzed using EDS-
energy dispersion method and Rutherford back scat-
tering of 4Не+ ions. These methods are comple-
mentary. Research results of the elemental compo-
sition of coatings are shown in fig. 1 and fig. 2.
Spectrum analysis of Ti-Hf-Si-N coating indi-
cates the absence of oxygen, nitrogen is 48.64 at.%,
34.35 at.% titanium, 4.49 at.% silicon, 7.83 at.%
hafnium (fig. 1). The presence of niobium 0.24 at.%
was found that is connected with purity hafnium and
the presence of 4.45 at.% iron. The analysis carried
out by Rutherford back scattering of 4Не+ ions
(fig. 2) shows that the coating composition is some-
what different from the composition obtained pre-
vious microanalysis. It is well known that RBS meth-
od is an etalon for the determination of concentra-
tion of the elements with high atomic number and
films thickness.
It is well known that RBS method is nondestruc-
tive and this is its advantage. At the same time SIMS
is more sensitive method (threshold of sensitivity is
about 10−6 at.%). Comparison of results obtained
by the RBS, SIMS and SIMS with a glow discharge
methods allows obtaining of more reliable data of
the elemental composition on the depth layer syn-
thesized coatings. The application of these methods
has made it possible to analyze composition along
Fig. 1. EDS spectrum of coatings on the basis Ti-Hf-Si-N
obtained by vacuum-arc deposition: UHF = –100 V,
Р = 0.3 Pа.
Fig. 2. RBS spectra o f Не+ with 1.3 MeV energy obtai-
ned from steel sample with Ti-Hf-Si-N coating: curve
1 − potential -100 V, P = 0.3 Ра, curve 2 − potential –200 V,
P = 0.7 Ра.
V.V. GRUDNITSKIY, V.M. BERESNEV, А.А. DROBYSHEVSKAYA, P.V. TURBIN, I.N. TORYANIK, S.S. GRANKIN, D.А. KOLESNIKOV, U.S. NEMCHENKO
288
the film cross-section from the surface to the film-
substrate interface including uncontrolled impurities
O and C appearing from the residual atmosphere in
the chamber in which the deposition of films carried
out. In fig. 3a, b the profiles of the elements includ-
ed in the coating composition Ti-Hf-Si-N, obtained
by using the RBS (including uncontrolled impurity)
are shown.
Presented profiles are built without the results of
SIMS analysis. As is seen from the presented re-
sults the oxygen in the coating is only in the surface
layer of thickness up to 10 ÷ 12 nm when coating
thickness is above a micron. The results of SIMS
analysis obtained for the same coating are present-
ed in fig. 4.
For samples with Ti-Hf-Si-N coating (P = 0.3
Pa, UHF = 100 V) the first series is received (fig. 2)
with the following stoichiometry of film: Ti − 40.0
at.%; Hf − 9.0 at.%; Si − 8.0 at.%; N − 43.0 at.%
when the film thickness is (1 ± 0.012) µm (fig. 4).
By increasing impulse bias potential up to 200 V
and changing the nitrogen pressure in the chamber
to 0.7 Pa the second series of samples with films
based on Ti-Hf-Si-N (Ti − 28.0 at.%; Hf − 18.0
at.%; Si − 9.0 at.%; N − 45.0 at.%) is received.
a)
b)
Fig. 3. The depth profiles of elements of the Ti-Hf-Si-N
coating obtained from RBS spectrums considering that
atomic density of layer is close to atomic density of
titanium nitride.
a)
b)
Fig. 4. SIMS analysis profiles of elements in the Ti-Hf-
Si-N coating obtained under concentrations of Ti – 40.0
at.%, Hf – 9.0 at.%, Si – 8.0 at.%, N – 46.0 at.% (first
series): а) – at.%, standard scale of concentration; b) –
logarithmic scale of concentration.
ELEMENTAL AND PHASE ANALYSIS OF NANOCOMPOSITE COATINGS ON BASIS Ti-Hf-Si-N SYSTEM RECEIVED BY THE VACUUM-АRC...
ФІП ФИП PSE, 2012, т. 10, № 3 vol. 10, No. 3
289ФІП ФИП PSE, 2012, т. 10, № 3 vol. 10, No. 3
The presented experimental result explained by
an increase pressure working gas (nitrogen) which
causes smooth decrease of silicon concentration
caused by that the average kinetic energy of emit-
ted from the cathode of titanium ions (122 eV) is
higher than that of silicon ions (97 eV) on the one
hand [4]. Thus as a result of collisions with gas tar-
gets there is “impoverishment” of the plasma flow
less energetic particles. On the other hand to this
process also contributes the selective silicon sput-
tering by the incident particle flux [5]. With further
increase of the nitrogen pressure is rather steep in-
crease of the Si content in the coating. That is in-
crease of value of the potential bias on the substrate
affects the energy value of condensed particles and
the concentration of silicon.
Research of the surface morphology of Ti-Hf-
Si-N coatings at concentration Ti − 40.0 at.%; Hf −
9.0 at.%; Si − 8.0 at.%; N − 43.0 at.% (thickness
4.0 µm) showed that the surface coating is present
drop component (fig. 5а). It is known [6] that the
coatings deposited at different pressures of nitro-
gen have different level of internal stress: high
microhardness is usually accompanied by higher in-
ternal stresses that actively relax (fig. 5b).
A comparison of the surface morphology of the
samples obtained at different partial pressures of
nitrogen indicates that in comparison with coatings
obtained at a nitrogen pressure P = 0.3 Pa the drop
component at P = 0.7 Pa decreases (fig. 6) . Thus
increasing the pressure of the reaction nitrogen me-
dium leads to a decrease in the number and size of
macroparticles that is to reduce the roughness of
coatings.
Presence in the vacuum chamber of active reac-
tion gases determines the formation with the vapor-
ized material of refractory compounds. In our case
the nitrides in the surface layer of the coating are
formed that determines its thermalphysical proper-
ties.
The above results show that in the case of low
thermal conductivity of the sputtered material which
is characteristic as titanium and hafnium (λ400(Ti) =
20 W/(m⋅K), λ400(Hf) = 22 W/(m⋅K)) [7] the gen-
a)
Fig. 5. The surface morphology of the coatings obtained
at a partial pressure of nitrogen PN = 0.3 Pa: a) − the coating
surface structure; b) − areas with delamination interlayer
of coating.
b)
a)
b)
Fig. 6. The surface topography of coatings based on
Ti-Hf-Si-N: a) P = 0.3 Pa, UHF = –200 V; b) − P = 0.7 Pa,
UHF = –200 V.
V.V. GRUDNITSKIY, V.M. BERESNEV, А.А. DROBYSHEVSKAYA, P.V. TURBIN, I.N. TORYANIK, S.S. GRANKIN, D.А. KOLESNIKOV, U.S. NEMCHENKO
290
eration of macroparticles is increased that leads to
high density of drop fraction in coatings.
The use of separated ion-plasma flow in order
to minimize the drop component in the coating [8,
9] offers great opportunities for deposition coatings
on precision machine parts. The separation of the
flow reduces the amount of macroparticles that gives
the coated product high physical and mechanical
properties thereby improving its functional charac-
teristics.
Thus it can be concluded that by changing the
physical and technological parameters of deposi-
tion (pulsed HF bias potential, the partial pressure
of nitrogen) can affect the surface morphology dur-
ing the formation of coatings and change percent-
age content of the coating components.
PHASE COMPOSITION OF NANOCOMPO-
SITE COATINGS ON BASIS Ti, Hf, Si and N
Prior to analysis of XRD data it should be noted
that for better understanding of processes occurred
at near-surface region during deposition it is neces-
sary to compare formation heats of the probable
nitrides.
According to [10] standard heats of formation
of such nitrides are next: ДH298(HfN) = −369.3 kJ/
mole, ДH298(TiN) = −336.6 kJ/mole, ДH298(Si3N4)
= −738.1 kJ/mole.
I.e. values of the formation heats are quite large
and negative. It indicates high probability of those
systems formation during all stages of transport of
the material from target to substrate. In addition,
proximity of formation heats for TiN and HfN es-
tablish conditions for formation of the sufficiently
homogenous (Ti, Hf)N solid solution.
The XRD-analysis revealed the formation of a
two-phase system in coatings. This system was de-
termined as the substitutional solid solution (Ti, Hf)N
because diffractions peaks of this phase are located
between peaks related to mononitrides TiN (JCPDS
38-1420) and HfN (JCPDS 33-0592). The diffused
peaks with less intensity at 2и values from 40° to
60° are related to the α-Si3N4 phase (fig. 7).
The results of the effect of technological param-
eters on the structural state of coatings based sys-
tem Ti-Hf-Si-N are represented in tabl. 1.
The analysis of the XRD data (see tabl. 1) shows
that by the characteristic structural features the coa-
tings obtained from the target of the same composi-
tion are very different depending on the conditions
of formation (the uniflow plasma flow or separated)
and technological deposition parameters which is
manifested in change of the average crystallite size
and the amount of Hf in the coating.
From X-ray diffraction spectra analysis (fig. 7)
follows that at uniflow regime of the plasma flow
non-textured polycrystalline coatings with significant
relative intensity of the peaks are formed. Rather
high intensity of the peaks at XRD-patterns of (Ti,
Hf)N solid solutions is attributed to relatively large
Fig. 7. XRD spectra of the coatings deposited on a steel
substrate at regimes: (23) –100 V, magnetic separated;
(28) –200 V, uniflow beam; (35) – 100 V, uniflow beam;
(37) –200 V, magnetic separated.
Table 1
Characteristics of the investigated Ti-Hf-Si-N coatings
№ Nitrogen pressure
in chamber (P), Ра
Potential bias,
V
Lattice parameter,
nm
Average size of
crystallite, nm
Hf content in solid
solution (Ti, Hf)N,
аt. % 1)
Notes
23 0.7 –200 0,4290 6.7 19 separation
37 0.6 –100 0,4337 5.0 33 separation
31 0.3 –200 0.4370 3.9 45 separation
35 0.6 – 0.7 –100 0.4337 4.3 69 uniflow beam
28 0.6 – 0.7 –200 0.4430 4.0 65 uniflow beam
1) Calculation was carried out according to Vegard rule from period values of solid solution (the influence of macrostresses
on the change of diffraction lines was not taken into account).
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concentration of hafnium, which has larger reflec-
tance value than titanium.
In case of beam separation the coatings have
different texturation. At low substrate potential
(100 V) coatings have [110] texture, and coatings
consist of textured and non-textured crystallites. The
volume content of textured crystallites is about 40%
of total amount of the crystallites and their lattice
parameter enlarged in comparison to non-textured
crystallites. The most likely reason for the increase
the lattice period can be the inhomogeneous distri-
bution of the hafnium atoms in coating (mainly in the
lattice sites of the textured crystallites).
At the same time the formation texture leads to
increasing of the average grains size of the crystal-
lites along the direction of incidence the film-forming
particles (perpendicular to the growing surface). For
example, in non-textured fraction of the crystallites
the average grains size is about 6.7 nm, whereas in
textured crystallites the value of the average grains
size is substantially more, namely 10.6 nm.
In the case of increasing the voltage to 200 V
the schemes with separation of ion-plasma flow were
used. In this case the coatings with reduced aver-
age crystallite size (up to 5 nm) were formed and
significantly decreased the fraction of textured crys-
tallites (less than 20% vol.). In this case texture axis
was defined as {001}.
Note that the increase of the accelerating volt-
age from 100 to 200 V (i. e. the energy increase of
the plasma flow) is characterized by identical values
the lattice period of the crystallites for both textured
and non-textured fractions. However the lattice pe-
riod in this case exceeds period for non-textured
fraction when applying a low potential to the sub-
strate and is 0.4337 nm.
According to Vegard law the value of the lattice
period corresponds to 33.0 аt.% of Hf in metal-
lic (Hf, Ti)N solid solutions of the nitride phase
(the reference data of the lattice periods of а
TiN = 0.424173 nm (JCPDS 38-1420) and а
HfN = 0.452534 nm (JCPDS 33-0592) were used).
However, as a rule, the compressive stresses in
coatings caused the decrease of the angles of cor-
responding diffraction peaks during и ÷ 2и scan
hence calculated values of lattice period can be over-
estimated. As a result inaccuracy of the calculation
of Hf concentration in solid solutions can achieve
about 5 ÷ 10 аt.%. Therefore presented results can
be considered as estimation of upper limit of the Hf
concentration in solid solution.
If we compare the phase-structural state of the
coatings produced at high pressure nitrogen
(PN = 0.3 Pa, the bias voltage UHF = −100 V) with
the largest lattice period in a relaxed state
a = 0.4437 nm (the maximum value of the lattice
period studied in this paper coatings apparently de-
termined by the highest content of hafnium atoms
and high pressure) then it is a significant change in
the phase-structural state of the coating.
All above mentioned results are related to sam-
ples obtained at typical pressure 0.6 ÷ 0.7 Pа. In a
case of coating deposition at −200 V substrate po-
tential in mode of separation (set of samples 31) the
decreasing of pressure up to 0.3 Pа caused the in-
crease of relative content of heavy Hf atoms in coat-
ings (tabl. 1). In addition, the average grains size of
the crystallites decreased with pressure.
Observed in this case the effects can be associ-
ated with an increase in of the radiation factor with
decreasing operating pressures. Indeed, the decrease
in pressure should be accompanied by decrease of
the probability of energy loss of atoms during colli-
sion between targets and substrate. Thus atoms at
substrates have relatively high energy which can pro-
mote secondary sputtering and radiation defect for-
mation. So, secondary sputtering leads to decrease
of relative content of heavy Hf atoms, while radia-
tion defect formation provide the decrease of grain
size with the increase of nucleus amount.
The coatings obtained under the typical pressure
0.6 ч 0.7 Pа in case of non-separated beam (di-
rect-flow mode) have considerably larger lattice
parameter; it can be explained by the high concen-
tration of heavy Hf atoms (tabl. 1). Apparently, the
more intensive direct-flow mode leads to the in-
crease of the nucleus density and hence to the de-
crease of average grain size. In addition, more pro-
nounced decrease of the grains size is caused by
the higher substrate potential 200 V. It is obviously
because increasing of radiation factor leads to the
dispersion of structure [12].
In the case of pulsed HF stimulation mikrode-
formation of the crystallites is less. In this case com-
pressive macrodeformation defined according to the
X-ray tensometry from “а-sin2ψ”-graph is connect-
ed in such condensates with manifestation of “atomic
peening” effect [11]. Crystallites of (Ti, Hf) N solid
solution in the coating based on Ti, Hf, Si and N are
under action of compressive elastic macrostresses
of system “condensate-substrate” (fig. 8).
V.V. GRUDNITSKIY, V.M. BERESNEV, А.А. DROBYSHEVSKAYA, P.V. TURBIN, I.N. TORYANIK, S.S. GRANKIN, D.А. KOLESNIKOV, U.S. NEMCHENKO
292
The research of Ti-Hf-Si-N coating in a trans-
mission electron microscope showed that the order
of the size of nanograins is corresponds to the data
XRD-analysis, namely, ultradispersive structure with
an average size of the crystallites within 5 ÷ 10 nm
is formed. Dark-field image of such a structure is
shown in fig. 9.
Differences in phase state and structure of thin
coatings deposited on the steel silicon substrates are
not found.
Great interest is the information about the fea-
tures of deformation in relation to multicomponent
coatings with nanocrystalline structure. Scanning
microscope Quanta 600 is used for fractographic
studies. The cracks surface passing through pricks
inflicted by the indentation (at loads F = 0.1 N and
F = 0.25 N) is studied. The appearance of fracture
surfaces of Ti-Hf-Si-N system thickness of 1.2 mi-
crons is shown in fig. 10. Measurements were car-
ried out device 402 MVD (Instron) at loads
F = 0.1 N and F = 0.25 N.
Fig. 8. X-ray picture of coating based on Ti-Hf-Si-N
(Р = 0.7 Pа): 1 − U = –100 V, <ε> = −1.9 %, а = 0.435 nm;
2 − U = –200 V, <ε> = −1.6 %, а = 0.431 nm.
b)
а)
Fig. 9. Photographs of the structure sections of the nano-
composite coating based on the Ti-Hf-Si-N solid solution
obtained using a transmission electron microscope: a) −
surface structure, b) − dark-field image of nanostructure
(transmission electron microscope JOEL 2010 F).
а)
b)
Fig. 10. Fraktograms of crack of Ti-Hf-Si-N film:
а) – F = 0.1 N; b) – F = 0.25 N.
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Looking at the nature of the impression and the
fracture plane the deformation is sufficiently uniform.
When using large loads F > 0.1 N at indentation on
the surface of the impression ring and radial cracks
are fixed (Fig. 10b) which can be observed when
measuring the hardness of fragile bodies, but the
formation of steps shift was not observed. Features
of deformation of thin coatings based on Ti-Hf-Si-
N can be related with the structure. The deforma-
tion is performed by sliding relative to each other of
individual columnar structure elements. For the in-
vestigated coatings typically clearly expressed co-
lumnar structure is characteristic and it is obvious
homogeneous indenter sliding along the columns.
Can also note that the investigated objects by their
nature are fragile and by nature the fracture are
intercrystalline [13, 14].
CONCLUSIONS
1. The elemental composition of coatings obtained
by vacuum-arc deposition with the use of pulsed
HF voltage of Ti-Hf-Si-N system depends on
the nitrogen pressure and HF potential applied
to the substrate. The coatings are formed on the
basis of a two-phase system: the first phase of
the solid solution (Ti, Hf) N and quasiamorphous
phases б-Si3N4 and HfSi2-nc.
2. The size of the nanocrystallites of the solid so-
lution of nanostructured coating (Ti, Hf)N is
changed from 3.8 to 10.6 nm. Interlayer of
б-Si3N4 surrounding nanograins of the solid so-
lution has a thickness ∼ 0.8 ÷ 1.2 nm.
3. Crystallites of the solid solution (Ti, Hf)N in the
coating based on Ti-Hf-Si-N are under action
of compressive elastic macrostresses of system
“condensate-substrate”. Compressive stresses
in the plane of condensate growth determine the
development of compression deformation of the
crystal lattice reaching a value of 1.9%.
4. The obtained multicomponent films have clear-
ly expressed columnar structure which is clearly
seen at the deformation. It is shown that the de-
formation of films Ti-Hf-Si-N at indentation is
performed by sliding columnar elements of the
structure parallel to the applied load, i.e. the
grain-boundary sliding is the main deformation
mechanism.
5. This work was partially performed within the
state budget research work № 0110U001257
funded by the Ministry of Education and Sci-
ence, Youth and Sports of the Ukraine as well
as under the state contract № 16.552 11 7004
with the financial support of the Ministry of Ed-
ucation of the Russian Federation. The authors
are grateful to Professor A.D. Pogrebnjak
(Sumy State University) and to Professor O.V.
Sobol (National Technical University “Kharkiv
Polytechnic Institute”) for a discussion of the
results.
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