Features of the formation and nanostructure of the film with the basic hexagonal phase TiN<sub>0.3</sub> by arc evaporation

doi:10.4236/jbpc.2011.21004

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Vol.2, No.1, 26-31 (2011)

doi:10.4236/jbpc.2011.21004

Journal of Biophysical Chemist ry

Features of the formation and nanostructure of the film

with the basic hexagonal pha se TiN0.3 by arc evaporation

Anna L. Kameneva1, L’ybov N. Gu selnikova2, Tatyana O. Soshina2

1State educational institution of the higher vocational education Perm state technical university, PSTU, Perm, Russia;

*Corresponding author: annkam789@mail.ru

2Branch of PSTU, Lys’va, Russia

Received 27 September 2010; revised 21 October 2010; accept 3 November 2010.

ABSTRACT

Forming and nanostructuring processes of TiN

film by electric arc evaporation under the condi-

tions of the reactive nitrogen gas deficit in the

gas mixture (30%) have been investigated. The

results of a technological experiment, electron

microscopic examination, X-ray diffraction phase

analysis and mechanical testing of the film re-

vealed that a significant increase in ion density

and mobility leads to deterioration of the

formation temperature condit ions, structural and

phase changes in TiN film and change of the main

cubic phase (111)TiN on a hexagonal (101)TiN0.3.

In the end repeated decrease of the the film mi-

crohardness with (101)TiN0.3 was caused not

only by erosion of the film, but also because of

change in the processes of its formation and

nanostructuring in comparison with similar

processes of the film with (111)TiN.

Keyw ords: TiN Film; Arc Spraying; Forming and

Nanostructuring Processes; Structure and Phase

Modification

1. INTRODUCTION

It is known [1-27] that films’ exploitation conditions

depend on raw materials, methods and technological

parameters of the application, providing the necessary

energy mass transfer of precipitable atoms, ions, mole-

cules, nano and ionized particles. The main technologi-

cal parameters are: the pressure of the gas mixture, the

bias voltage on the substrate, the contents of the reaction

gas in the gas mixture, the cathode-substrate distance,

arc current (for electric arc evaporation), the temperature

of the substrate and film, the maximum rate of deposition.

The aim of this paper is to study the effect of the ni-

trogen minimum concentration in the gas mixture at the

temperature conditions, the direction of preferential crys-

tallographic orientation, phase composition, mechanical

conditions, formation and nanostructuring of TiN film

during electric-arc evaporation.

2. METHODS OF THE SUBSTRATES

PREPARATION, FORMING AND

INVESTIGATION OF STRUCTURE

AND CONDITIONS OF TiN FILM

2.1. Methods of the Preparation of

Substrates and Formation of TiN Film

TiN film was formed on an industrial installation

NNV-6.6-I4 with a single arc evaporation with a tita-

nium cathode (s BT1-00) with 30% nitrogen content in

the gas mixture. To increase the adhesive strength of TiN

film on the surface of the test samples from Article 2 [2],

Ti underlayer was applied after its ion cleaning- heating.

2.2. The Method of Substrate and TiN Film

Temperature Control

Temperature of test pieces surface as well as the film

temperature after each 10 minutes of the film deposition

have been measured by infrared contactless pyrometer

after both ionic cleaning and sublayer applying, a whole

duration of the precipitation process was 30 minutes.

2.3. Methods of Studying the Structure,

Phase Composition and Conditions

of TiN Film

Morphological traits of the formed films have been

investigated by bitmapped electron microscope BS 300

with prefix for microanalysis EDAX Genesis 2000.

X-ray diffraction phase analysis of TiN film was carried

out using X-ray diffractometer DRON-4 in Cu Kα radia-

tion. Microhardness of the composition has been meas-

ured by microhardness tester PМТ-3 with indenter load

A. L. Kameneva et al. / Journal of Biophysical Chemistry 2 (2010) 26-31

of 0.5 N after the film precipitation process.

3. SIMULATION RESULTS AND

DISCUSSION

Technological parameters of processes for preparing

the substrate surface before precipitation process of the

film: ion cleaning- heating and deposition of Ti under-

layer are shown in Table 1, the technological parameters

of electric arc evaporation process and microhardness of

the composition: the TiN film - substrate (hereinafter the

microhardness of the composition) are listed in Table 2.

The results of X-ray diffraction phase analysis of

TiN film plots, formed by arc evaporation at a nitrogen

content in the gas mixture of 30% do not correspond

with the previous similar studies of TiN film, formed at

different contents of bias potential on the substrate

(Figure 1, Tables 3,4). It was found previously [2] that

regardless of the bias voltage at a maximum tempera-

ture of the film > 700 K and the rate of heating on the

substrate > 14.2 K/min, the film is formed, consisting

of the main cubic phase of TiN with the direction of

preferred crystallographic orientation (111) and more -

hexagonal phase TiN0.3.

It was established for the first time that the nitrogen

content decrease in the gas mixture to 30%, a significant

increase in ion density and its mobility, as well as dete-

rioration of the formation temperature conditions (the

original film temperature was 613 K, the rate of its heat-

ing - 12.0 K/min) lead to a change in the basic cubic

phase 111(TiN) to the hexagonal (101)TiN0.3 phase, the

emergence of new additional phases with volume frac-

tions: tetragonal Ti2N - 3.7% and hexagonal Ti - 2.1%

and more than twofold decrease of the composition mi-

crohardness. It ought to be noted that minimal deviation

of the interplanar distance from the table value, a maxi-

mum width of the peaks of the hexagonal phase

(101)TiN0.3 and homogeneous internal stresses in the

film happened due to unidirectional displacement of the

peaks (111)Ti2N and (101)TiN0.3, (111)Ti.

To determine the cause of changes in the mechanical

conditions of TiN film, based on the structural charac-

teristics and phase composition, which differs from all

previously received TiN film, the morphological features

of its surface were studied.

Through a small increase it was possible to find out

only the rough surface of TiN film (Figure 2).

Based on the results of electron microscopic studies of

the film surface at higher magnification it was revealed

that the formation and nanostructure processes of the

film with the basic hexagonal TiN0.3, or cubic TiN phase

are different. In constructed thermal conditions two

processes consistently occur: the formation of coarse-

grained film and when the temperature of the film gets

close to 700 K (650 K) - nanostructuring polycrystalline

part of the film.

When the initial temperature conditions of formation

is 613 K and heating rate is 12.0 K/min coarse-grain film

of laminose structure is formed (Figure 3). Erosion of

the film surface and its maximum surface roughness, as

a result of intense bombardment and sputtering lead to

Table 1. Process conditions of ion cleaning- heating and deposition of Ti underlayer.

Process U, V

Substrate - plazma source

distance, mm T, minP, PaIfocusing coil, AIstabilizing coil,

Iarc,

rpm GasFinal temperature,

Ionic cleaning high 600 270 5 0.01 1.50 2.50 80 2.5 Ar 651

Sublayer applying bias 200 270 3 1.0 1.50 2.50 80 2.5 Ar 613

Table 2. Process conditions of the TiN film applying.

Table 3. Structural characteristics of the TiN-based films produced by arc spraying. V is phase inclusion volume fraction,

dTi2N/dTi2Ntable is cleavage spacing, ITi2N/ITiN0,3 is intensity ratio of all reflexes of tetragonal Ti2N phase and hexagonal TiN0,3 the one,

maxI111Ti2N/IΣ and maxI101TiN0.3/IΣ are ratios of maximum reflex intensities (111) or (101) to total intensity of all TiN phase reflexes,

and β0 is breadth of X-ray diffraction line.

V, %

Ti Ti2N TiN0,3

dTi

dTitable, nm

dTi2N

dTi2Ntable,

dTiN0,3

dTiN0,3table, nm

ITi

ITiN0,3

ITi2N

ITiN0,3

IΣ max

I002Ti

IΣ

max I

111Ti2N

IΣ

maxI

101TiN0,3

IΣ

max ITi

max ITiN0,3

β0111

β0101

2.1 3.7 94.2 0.2353

0.2340

0.2298

0.2292

0.2271

0.2268

0.03 0.08 119.50.03 0.07 0.90 0.07 0.67

1.41

N2, % L, mm P, Pa Iarc, A Ubias, V Tfilm, K Vfilm heat, Hμ, GPa

tprocess = 10 mintprocess = 20

min

tprocess = 30

min K/min

30 270 1.0 80 200 625 635 660 12.0 10.0

A. L. Kameneva et al. / Journal of Biophysical Chemistry 2 (2010) 26-31

Table 4. Positions of the diffraction peaks.

Film Phase Lattice type Grain orientation 2θтабл, grad 2θ, grad

Ti Hexagonal <002> 38,3911 38,25

Ti 2N Tetragonal <111> 39,3267 39,20

TiN

Ti N0,3 Hexagonal <101> 39,7086 39,649

Figure 1. Comparative band of diffractogram fragments for TiN-based film pieces produced by arc spraying with 30% nitrogen

content in the gas mixture.

defects in the form of discontinuity at the interface of

grains (Figure 4(a)), cracking (Figure 4(b)), grain pit-

ting (Figure 4(c)), and grain boundary fracture of the

film Figur e 4( d)).

It was discovered for the first time that film tempera-

ture increase up to 650 K leads to change of processe

from coarse-grain film formation to nanostructuring of

the polycrystalline film constituent, connected with the

following indispensable stage consequence.

z Forming of the globules (Figure 5(a)).

z Integration of the globules (Figure 5(b)) followed

by surface texturing at the end (Figure 5(c)).

z Forming of 3D- formations with grain substructure

(Figure 5(d)).

z Surface coarsening of the 3D- formations with

grain substructure (Figure 5(e)).

z Nucleation of polycrystalline constituent of the film

(Figure 5(f)).

z Nanostructuring of the film polycrystalline con-

stituent (Figure 5(g)) followed by seed integration to

microsystems with incoherent boundaries (Figure 5(h)).

z Forming of cone textures <111> on the surface of

the 3D-formations with laminose structure (Figure 5(i)).

The whole process of nanostructuring polycrystalline

constituent of the film is shown in Figure 6.

5. CONCLUSION

Phase-structural state of TiN film, formed by electric

arc evaporation with a minimum content of nitrogen in

the gas mixture (30%) was investigated by X-ray dif-

Figure 2. Photomicrographs of TiN films formed

by arc spraying at 30% nitrogen concentration in

mixed gas.

A. L. Kameneva et al. / Journal of Biophysical Chemistry 2 (2010) 26-31

(а) (b)

Figure 3. Photomicrograhs of continuous coarse-grained film (a) having laminar grains (b).

(а) (b)

Figure 4. Photomicrographs of TiN film formed at minimum nitrogen concentration (30%) in mixed gas. The film has surface

defects: (a) Discontinuity on grain interface; grain (b) Cracking and (c) Roughening; (d) Grain-boundary film destruction, max

grain dimensions are 4.5 × 29.0 μm; (e) Discontinuity (“lack”) of the film material.

fraction phase analysis method. For the first time ever

was established that the maximum possible content of

argon in the gas mixture leads to a change in the main

phase of the film from a cubic (111)TiN to the hexagonal

(101)TiN0.3.

Results of electron-microscopic studies of the films

surface morphology revealed that at the film temperature

less than 650 K coarse-grained film with various defects

is formed on the substrate surface. Nanostructuring

process of polycrystalline constituent of the film with

the main hexagonal TiN0.3 phase differs from the same

film process with the main cubic (111)TiN phase.

Based on previous experimental studies of the struc-

ture and conditions of films formed by nitrogen content

in the gas mixture of 90% and a variable bias to the sub-

strate 80 ... 250 V was found that the nucleation of a

polycrystalline film with the main component of the

cubic phase (111)TiN occurs only at temperatures of

films > 700 K and the rate of heating > 14.2 K/min [2].

The obtained results allow to suggest that the main

reason for changing the phase ratio in the film, the orig-

inal course of the process of coarse-grained film forma-

tion, and then the process of nanostructuring of poly

crystalline constituent of the film with the main compo-

nent of the hexagonal phase (101)TiN0.3, under conditions

of low nitrogen content and intensity ion bombardment

of the surface forming a film by argon is in sufficient

temperature conditions, characterized by the temperature

A. L. Kameneva et al. / Journal of Biophysical Chemistry 2 (2010) 26-31

(а) (b) (c)

(d) (e) (f) (g)

(h) (i)

Figure 5. Photomicrograhs of the film having main hexagonal TiN0.3 phase on various stages: (a) globular with

globule dimension up to Ø9.0 μm; (b) integration of the globules with maximum dimensions of Ø7.5 μm and Ø6.5

μm into structures with length L = 14.0 μm and/or (c) integration of the globules into islands dimensioned up to

Ø17.0 μm having globular structure; forming of 3D formations with grain substructure (d) and further their sur-

face coarsening (e) (respectively Ø12.0 μm and Ø9.0 μm); (f) forming of seeds of polycrystalline constituent of

the film having form of frustums with upper base dimension of 120x250 μm; (g) forming of laminar 3D forma-

tions (Ø4.0 μm) sustaining border coherence, (h) their integration into laminar microsystems (Ø9.0 μm) having

non-coherent borders and discontinuity, (i) forming of conic surface structures <111>.

Figure 6. Stages of nanostructuring of TiN films with main hexagonal TiN0.3 phase by arc spraying method (~ 660

K, 30% N2,Vfilm heating = 12.0 K / min).

of the film and its rate of heating, nucleation,formation

and nanostructure of the film with the main cubic phase

(111)TiN.

We can assume that one of the main reasons for dou-

ble reduction in the microhardness composition is dif-

ferent structural states of formed continuous film-grain

lamellar structure and formed on its surface as a result of

nanostructuring 3D structures with a lamellar substruc-

ture.

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