Titanium nitride based coatings are very attractive for protection of materials in extreme conditions.
However, their behavior under different kinds of irradiation is not entirely well understood. In this work,
the influence of ion-implanted deuterium on changes of the structure and mechanical properties TiZrN,
TiAlSiN, TiAlYN films were investigated. Films were deposited by filtered vacuum arc plasma technique.
After deposition all films were irradiated at room temperature with 12 keV D+ ions to dose 1 1018 D/cm2.
Composition, structure and nanohardness of the coatings were determined by X-ray fluorescence method,
X-ray diffraction and nanoindentation. The effusion of the implanted deuterium was studied by thermal
desorption spectroscopy.
It is shown that irradiation by deuterium ions does not make structural changes in multicomponent
films. Deuterium thermal desorption spectrum of various coatings are substantially different. Nanohardness
of all investigated coatings after irradiation and thermal desorption are decreased.
When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3545

Belous, V.A.

Kuprin, A.S.

Lomino, N.S.

Morozov, O.M.

Ovcharenko, V.D.

Reshetnyak, E.N.

Tolmachova, G.N.

Zhurba, V.I.

Electronic Sumy State University Institutional Repository

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE NANOMATERIALS: APPLICATIONS AND PROPERTIES Vol. 1 No 4, 04RES07(3pp) (2012)   2304-1862/2012/1(4)04RES07(3) 04RES07-1  2012 Sumy State University Influence of Deuterium Ion Implantation on the Structure  and Hardness of Nanocrystalline Films  V.A. Belous, A.S. Kuprin*, N.S. Lomino, V.D. Ovcharenko, E.N. Reshetnyak, O.M. Morozov, V.I. Zhurba,  G.N. Tolmachova  National Science Center “Kharkov Institute of Physics and Technology”, 1, Akademicheskaya St., Kharkov, Ukraine  (Received 20 June 2012; published online 24 August 2012)  Titanium nitride based coatings are very attractive for protection of materials in extreme conditions. However, their behavior under different kinds of irradiation is not entirely well understood. In this work, the influence of ion-implanted deuterium on changes of the structure and mechanical properties TiZrN, TiAlSiN, TiAlYN films were investigated. Films were deposited by filtered vacuum arc plasma technique. After deposition all films were irradiated at room temperature with 12 keV D+ ions to dose 1  1018 D/cm2. Composition, structure and nanohardness of the coatings were determined by X-ray fluorescence method, X-ray diffraction and nanoindentation. The effusion of the implanted deuterium was studied by thermal desorption spectroscopy. It is shown that irradiation by deuterium ions does not make structural changes in multicomponent films. Deuterium thermal desorption spectrum of various coatings are substantially different. Nanohard-ness of all investigated coatings after irradiation and thermal desorption are decreased.  Keywords: Vacuum arc, Nanostructured coatings, Hardness, Implantation, Deuterium, Thermal desorption.    PACS numbers: 61.80.Lj, 62.20.Qp, 68.43.Vx, 81.40.Wx                                                             * kuprin@kipt.kharkov.ua  1. INTRODUCTION  Multicomponent nanostructured coatings based on titanium nitride with the addition of the elements Zr, Al, Si, B, Cr, Y have a high hardness, corrosion resistance and thermal stability [1]. The study of the stability properties of nitride coatings with various types of radiation is an actual problem [2,3]. This paper presents the results of a study of hardness, structure and temperature ranges of desorption ion-implanted deuterium from multicomponent coatings based on TiN.  2. EXPERIMENT  TiN based coatings, with different concentration of alloying elements were deposited onto stainless steel substrates by filtered cathodic vacuum arc evaporation system from the Ti80Zr20, Ti78Al16Si06, Ti67Al28Y05 cathodes [4]. In all cases, a pure nitrogen atmosphere was used to deposit the coatings. The pressure during deposition was in the range of 0.04 – 0.8 Pa and the substrates were held at a bias of 100 V. The thickness of all the samples was approximately 3 m. Composition of the coatings was determined by X-ray fluorescence method. The phase composition and substructure of coatings were studied by X-ray analysis on a DRON-3 diffractometer in the filtered radiation from a copper anode. The processing of diffraction patterns produced by a computer program New_Profile. The crystallite size was determined from the broadening of the lines from the Selyakov-Scherrer relation. The hardness measurements were carried out on coatings using a Nanoindenter G200 equipped with a Berkovich diamond tip to penetration depth 300 nm by CSM method. Implantation of deuterium and thermal desorption spectroscopy measurements were performed in the experimental apparatus "SKIF", described in detail in [5]. Irradiation was carried by ions D + energy of 12 keV, at dose of 1  1018 D/cm2 at room temperature. The studies of thermal desorption spectrum of ion-implanted deuterium from coatings aged for 50 days at room temperature. The heating was carried out at an average rate 7 K/s to a temperature of 1500 K, with simultaneous recording of the spectrum of desorption D (4 amu). Temperature measurement was carried out tungsten-rhenium thermocouples WRe5/20 attached to the heater.  3. RESULTS AND DISCUSSION  After deposition, depending on the nitrogen pressure the samples had different elemental and phase composition. Fig. 1 shows the diffractograms of the coatings. In all diffraction patterns, in addition to the lines of the substrate, revealed a single line of the crystalline phase - nitride with fcc structure characteristic of TiN (structural type NaCl). It is seen that the number of detected lines of this phase, their intensity, position and width depend strongly on the composition of the cathode and the pressure of nitrogen. This demonstrates the significant differences in the structure of the films: the number of the crystalline phase, crystallite size, lattice parameter and texture. Displacement of the diffraction lines of nitrides relative positions of the lines of TiN due to the formation solid solutions and residual stresses in the films.   V.A. BELOUS, A.S. KUPRIN, N.S. LOMINO, ET AL. PROC. NAP 1, 04RES07 (2012)   04RES07-2   Fig. 1 – X-ray diffraction patterns of vacuum arc nitride coatings: S-substrate, 1 – Ti99Zr1N; 2 – Ti59Al37Si4N;  3 – Ti75Al21Si4N; 4 – Ti50Al48Y2N  Coating Ti99Zr1N has a well-formed crystalline structure with a characteristic columnar coatings axial texture [111] and the crystallite size  22nm. In the films, which include the aluminum content of the crystalline phase is much lower, and the size of the crystallites  10 nm. Depending on the composition of these coatings are characterized by amorphous or amorphous-crystalline structure. The composition, characteristics of the substructure and hardness of the films are shown in Table 1. Was found that irradiation of deuterium ions does not lead to significant changes in the structure of coat-ings. On the diffractograms of the samples after irradi-ation, no changes were detected. The exception is the coating Ti99Zr1N the diffraction lines is shifted toward smaller angles. Estimates show that the period of the crystal lattice nitride grown from 0,4309  0,0003 to 0,4321  0,0003 nm. This may be due to the dissolution of the deuterium in the nitride lattice. This is con-firmed by thermal desorption of deuterium form the spectrum (Fig. 2, curve 1). Table 1 – The composition, characteristics of the substructure and hardness of coatings  Coatings composition, at% Pressure, Pa Texture axis Crystallite size, nm Н, GPа as deposited Н, GPa irradiated Н, GPa after thermal desorption Ti99Zr1N 0,04 [111] 22 30 26 20 Ti59Al37Si4N 0,04 [110] 10 40 15 15 Ti75Al21Si4N 0,8 — 10 25 23 18 Ti31Al68Y1N 0,04 amorphous — 23 15 13 Ti50Al48Y2N 0,8 — 7 26 11 8     Fig. 2 – Thermal desorption spectroscopy of D2 ion implanted in coatings: 1 – Ti99Zr1N; 2 – Ti50Al48Y2N; 3 – Ti31Al68Y1N;  4 – Ti59Al37Si4N; 5 – Ti75Al21Si4N  Implanted deuterium forms a phase state of solid solution of deuterium in titanium and titanium nitride that is shown in the spectrum as two peaks with maximum temperatures of 1100 K and 1250 K. According to literature data low temperature peak almost exactly coincides with the temperature of a solid solution of deuterium in titanium [6], therefore high temperature peak due to the presence of the phase state of solid solution of deuterium in titanium nitride. Thermal desorption spectra of samples with a large number of components is much broader, more difficult, but the beginning of the deuterium yield is shifted towards lower temperatures. Especially strongly decreases the temperature started out to cating Ti75Al21Si4N and is  600 K. It appears that deuterium interacts with the amorphous component of the condensate, and its output is a multistep process with different activation energies. In contrast to the crystalline structure, hardness of the coating after irradiation is not retained (see Table. 1). Hardness of the coating Ti99Zr1N decreases from 30 GPa to 26 GPa after irradiation and up to 20 GPa after thermal desorption. For multicomponent coatings reducing the hardness is significant.  4. CONCLUSIONS  Deuterium ion irradiation dose of 1  1018 D/cm2 no significant structural changes in multicomponent films, a slight increase in the period observed in the crystal lattice Ti99Zr1N. High dose implantation of deuterium leads to a decrease in the hardness of coating, which remains relatively high (26 – 23 GPa) for coatings Ti99Zr1N, Ti75Al21Si4N. The structure of the thermal desorption spectrums of deuterium from the nitride coatings depends strongly on the composition of the component and indicates the presence of significant structural differences in the obtained coatings.  INFLUENCE OF DEUTERIUM ION IMPLANTATION ON… PROC. NAP 1, 04RES07 (2012)    04RES07-3  REFERENCES  1. S. PalDey, S.C. Deevi, Mater. Sci. Eng. A 342, 58 (2003). 2. H. Wang, R. Araujo, J.G. Swadener, Y.Q. Wang, X. Zhang, E.G. Fu, T. Cagin. Nucl. Instr. Meth. B 261, 1162 (2007). 3. V.V. Uglov, D.P. Rusalski, S.V. Zlotski, A.V. Sevriuk, G. Abadias, S.B. Kislitsin, K.K. Kadyrzhanov, I.D. Gorlachev, S.N. Dub. Surf. Coat. Technol. 204, 2095 (2010). 4. I.I. Aksenov, V.M. Khoroshikh, N.S. Lomino, V.D. Ovcharenko, Y.A Zadneprovskiy, IEEE T. Plasma Sci. 27, 1026 (1999). 5. V.V. Ruzhitsky, Yu.A. Gribanov, V.F. Rybalko, S.M. Khazan, I.S. Martynov, A.N. Morozov. Vopr. At. Nauki Tekhn. Ser. 4/51, 84 (1989). 6. I.M. Neklyudov, A.N. Morozov, V.G. Kulish. Materi-alovedenie No 11, 45 (2005).  

Influence of Deuterium Ion Implantation on the Structure and Hardness of Nanocrystalline Films

SocioEconomic Challenges Journal (Sumy State University)

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE NANOMATERIALS: APPLICATIONS AND PROPERTIES 
Vol. 1 No 4, 04RES07(3pp) (2012) 
 
 
2304-1862/2012/1(4)04RES07(3) 04RES07-1  2012 Sumy State University 
Influence of Deuterium Ion Implantation on the Structure  
and Hardness of Nanocrystalline Films 
 
V.A. Belous, A.S. Kuprin*, N.S. Lomino, V.D. Ovcharenko, E.N. Reshetnyak, 
O.M. Morozov, V.I. Zhurba,  G.N. Tolmachova 
 
National Science Center “Kharkov Institute of Physics and Technology”, 1, Akademicheskaya St., Kharkov, Ukraine 
 
(Received 20 June 2012; published online 24 August 2012) 
 
Titanium nitride based coatings are very attractive for protection of materials in extreme conditions. 
However, their behavior under different kinds of irradiation is not entirely well understood. In this work, 
the influence of ion-implanted deuterium on changes of the structure and mechanical properties TiZrN, 
TiAlSiN, TiAlYN films were investigated. Films were deposited by filtered vacuum arc plasma technique. 
After deposition all films were irradiated at room temperature with 12 keV D+ ions to dose 1  1018 D/cm2. 
Composition, structure and nanohardness of the coatings were determined by X-ray fluorescence method, 
X-ray diffraction and nanoindentation. The effusion of the implanted deuterium was studied by thermal 
desorption spectroscopy. 
It is shown that irradiation by deuterium ions does not make structural changes in multicomponent 
films. Deuterium thermal desorption spectrum of various coatings are substantially different. Nanohard-
ness of all investigated coatings after irradiation and thermal desorption are decreased. 
 
Keywords: Vacuum arc, Nanostructured coatings, Hardness, Implantation, Deuterium, Thermal desorption. 
 
  PACS numbers: 61.80.Lj, 62.20.Qp, 68.43.Vx, 81.40.Wx 
 
 
                                                          
* kuprin@kipt.kharkov.ua  
1. INTRODUCTION 
 
Multicomponent nanostructured coatings based 
on titanium nitride with the addition of the elements 
Zr, Al, Si, B, Cr, Y have a high hardness, corrosion 
resistance and thermal stability [1]. The study of the 
stability properties of nitride coatings with various 
types of radiation is an actual problem [2,3]. This 
paper presents the results of a study of hardness, 
structure and temperature ranges of desorption ion-
implanted deuterium from multicomponent coatings 
based on TiN. 
 
2. EXPERIMENT 
 
TiN based coatings, with different concentration 
of alloying elements were deposited onto stainless 
steel substrates by filtered cathodic vacuum arc 
evaporation system from the Ti80Zr20, Ti78Al16Si06, 
Ti67Al28Y05 cathodes [4]. In all cases, a pure nitrogen 
atmosphere was used to deposit the coatings. The 
pressure during deposition was in the range of 0.04 –
 0.8 Pa and the substrates were held at a bias of 
100 V. The thickness of all the samples was 
approximately 3 m. 
Composition of the coatings was determined by X-
ray fluorescence method. The phase composition and 
substructure of coatings were studied by X-ray 
analysis on a DRON-3 diffractometer in the filtered 
radiation from a copper anode. The processing of 
diffraction patterns produced by a computer program 
New_Profile. The crystallite size was determined 
from the broadening of the lines from the Selyakov-
Scherrer relation. The hardness measurements were 
carried out on coatings using a Nanoindenter G200 
equipped with a Berkovich diamond tip to 
penetration depth 300 nm by CSM method. 
Implantation of deuterium and thermal desorption 
spectroscopy measurements were performed in the 
experimental apparatus "SKIF", described in detail 
in [5]. Irradiation was carried by ions D + energy of 
12 keV, at dose of 1  1018 D/cm2 at room 
temperature. The studies of thermal desorption 
spectrum of ion-implanted deuterium from coatings 
aged for 50 days at room temperature. The heating 
was carried out at an average rate 7 K/s to a 
temperature of 1500 K, with simultaneous recording 
of the spectrum of desorption D (4 amu). 
Temperature measurement was carried out 
tungsten-rhenium thermocouples WRe5/20 attached 
to the heater. 
 
3. RESULTS AND DISCUSSION 
 
After deposition, depending on the nitrogen 
pressure the samples had different elemental and 
phase composition. Fig. 1 shows the diffractograms 
of the coatings. 
In all diffraction patterns, in addition to the lines 
of the substrate, revealed a single line of the 
crystalline phase - nitride with fcc structure 
characteristic of TiN (structural type NaCl). It is 
seen that the number of detected lines of this phase, 
their intensity, position and width depend strongly 
on the composition of the cathode and the pressure of 
nitrogen. This demonstrates the significant 
differences in the structure of the films: the number 
of the crystalline phase, crystallite size, lattice 
parameter and texture. Displacement of the 
diffraction lines of nitrides relative positions of the 
lines of TiN due to the formation solid solutions and 
residual stresses in the films. 
 
 V.A. BELOUS, A.S. KUPRIN, N.S. LOMINO, ET AL. PROC. NAP 1, 04RES07 (2012) 
 
 
04RES07-2 
 
 
Fig. 1 – X-ray diffraction patterns of vacuum arc nitride 
coatings: S-substrate, 1 – Ti99Zr1N; 2 – Ti59Al37Si4N;  
3 – Ti75Al21Si4N; 4 – Ti50Al48Y2N 
 
Coating Ti99Zr1N has a well-formed crystalline 
structure with a characteristic columnar coatings axial 
texture [111] and the crystallite size  22nm. In the 
films, which include the aluminum content of the 
crystalline phase is much lower, and the size of the 
crystallites  10 nm. Depending on the composition of 
these coatings are characterized by amorphous or 
amorphous-crystalline structure. The composition, 
characteristics of the substructure and hardness of the 
films are shown in Table 1. 
Was found that irradiation of deuterium ions does 
not lead to significant changes in the structure of coat-
ings. On the diffractograms of the samples after irradi-
ation, no changes were detected. The exception is the 
coating Ti99Zr1N the diffraction lines is shifted toward 
smaller angles. Estimates show that the period of the 
crystal lattice nitride grown from 0,4309  0,0003 to 
0,4321  0,0003 nm. This may be due to the dissolution 
of the deuterium in the nitride lattice. This is con-
firmed by thermal desorption of deuterium form the 
spectrum (Fig. 2, curve 1). 
Table 1 – The composition, characteristics of the substructure and hardness of coatings 
 
Coatings 
composition, at% 
Pressure, Pa Texture axis 
Crystallite 
size, nm 
Н, GPа as 
deposited 
Н, GPa 
irradiated 
Н, GPa after 
thermal 
desorption 
Ti99Zr1N 0,04 [111] 22 30 26 20 
Ti59Al37Si4N 0,04 [110] 10 40 15 15 
Ti75Al21Si4N 0,8 — 10 25 23 18 
Ti31Al68Y1N 0,04 amorphous — 23 15 13 
Ti50Al48Y2N 0,8 — 7 26 11 8 
 
 
 
 
Fig. 2 – Thermal desorption spectroscopy of D2 ion implanted 
in coatings: 1 – Ti99Zr1N; 2 – Ti50Al48Y2N; 3 – Ti31Al68Y1N;  
4 – Ti59Al37Si4N; 5 – Ti75Al21Si4N 
 
Implanted deuterium forms a phase state of solid 
solution of deuterium in titanium and titanium nitride 
that is shown in the spectrum as two peaks with 
maximum temperatures of 1100 K and 1250 K. 
According to literature data low temperature peak 
almost exactly coincides with the temperature of a solid 
solution of deuterium in titanium [6], therefore high 
temperature peak due to the presence of the phase 
state of solid solution of deuterium in titanium nitride. 
Thermal desorption spectra of samples with a large 
number of components is much broader, more difficult, 
but the beginning of the deuterium yield is shifted 
towards lower temperatures. Especially strongly 
decreases the temperature started out to cating 
Ti75Al21Si4N and is  600 K. It appears that deuterium 
interacts with the amorphous component of the 
condensate, and its output is a multistep process with 
different activation energies. 
In contrast to the crystalline structure, hardness of 
the coating after irradiation is not retained (see 
Table. 1). Hardness of the coating Ti99Zr1N decreases 
from 30 GPa to 26 GPa after irradiation and up to 
20 GPa after thermal desorption. For multicomponent 
coatings reducing the hardness is significant. 
 
4. CONCLUSIONS 
 
Deuterium ion irradiation dose of 1  1018 D/cm2 
no significant structural changes in multicomponent 
films, a slight increase in the period observed in the 
crystal lattice Ti99Zr1N. 
High dose implantation of deuterium leads to a 
decrease in the hardness of coating, which remains 
relatively high (26 – 23 GPa) for coatings Ti99Zr1N, 
Ti75Al21Si4N. 
The structure of the thermal desorption spectrums 
of deuterium from the nitride coatings depends 
strongly on the composition of the component and 
indicates the presence of significant structural 
differences in the obtained coatings. 
 INFLUENCE OF DEUTERIUM ION IMPLANTATION ON… PROC. NAP 1, 04RES07 (2012) 
 
 
 04RES07-3  
REFERENCES 
 
1. S. PalDey, S.C. Deevi, Mater. Sci. Eng. A 342, 58 (2003). 
2. H. Wang, R. Araujo, J.G. Swadener, Y.Q. Wang, X. Zhang, 
E.G. Fu, T. Cagin. Nucl. Instr. Meth. B 261, 1162 (2007). 
3. V.V. Uglov, D.P. Rusalski, S.V. Zlotski, A.V. Sevriuk, 
G. Abadias, S.B. Kislitsin, K.K. Kadyrzhanov, 
I.D. Gorlachev, S.N. Dub. Surf. Coat. Technol. 204, 2095 
(2010). 
4. I.I. Aksenov, V.M. Khoroshikh, N.S. Lomino, 
V.D. Ovcharenko, Y.A Zadneprovskiy, IEEE T. Plasma 
Sci. 27, 1026 (1999). 
5. V.V. Ruzhitsky, Yu.A. Gribanov, V.F. Rybalko, 
S.M. Khazan, I.S. Martynov, A.N. Morozov. Vopr. At. 
Nauki Tekhn. Ser. 4/51, 84 (1989). 
6. I.M. Neklyudov, A.N. Morozov, V.G. Kulish. Materi-
alovedenie No 11, 45 (2005). 
 


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Influence of Deuterium Ion Implantation on the Structure and Hardness of Nanocrystalline Films

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