Applied Mechanics and Materials Vols.

155-156 (2012) pp 291-297

Online available since 2012/Feb/27 at www.scientific.net
© (2012) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMM.155-156.291

Ab-initio Study of the phonon frequency, Electrical and Thermal

properties of TiN
Xin Tan1,2,a, Yuqing Li2,b, Xuejie Liu2,c
1
School of Mechanical Engineering and Automation, Northeastern University, Shenyang, 110004, PR
China
2
School of Mechanical Engineering, Inner Mongolia University of Science & Technology, Baotou 014010,
PR China
a
heart_tan@126.com, bpuffin2008@163.com, cxuejieliu2000@yahoo.com

Keywords: Ab initio calculations, Electronic structure, Phonon spectrum, Thermal properties, TiN

Abstract. With a motivation to understand microscopic aspects of TiN relevant to the electronic
structure, phonon and thermal properties of transition metal nitride TiN superlattices, we determine
its electronic structure, phonon spectra and thermal properties using first-principles calculations
based on density functional theory with a generalized gradient approximation of the exchange
correlation energy. We find that the electronic bands crossed by EF are half occupied, TiN has the
ability of taking part in chemical reactions and also has the surface activity; A large gap in its
phonon spectra, anomalies in the phonon dispersion of metallic TiN, manifested as dips in acoustic
branches, but it do not contain soft modes in any direction; The specific heat (Cv) of TiN rises
rapidly at low temperatures, the Cv values of the material, is identical to the Dulong-Petit value at
high temperatures. Under the quasi-harmonic approximation (QHA), the thermal expansion,
specific heat and bulk modulus B(T) are obtained, and the B(T) decreases along with the increase of
temperature.

Introduction
TiN is the fifth-column transition metal nitride, NaCl type face-centered cubic crystal structure. The
ionic bond, metallic bond and covalent bond coexist in its crystal, P orbitals of nitrogen energy is
lower than the Fermi level, which will result in the movement of free electrons is similar to the
metal d orbital movement [1,2]. This electronic structure determines that it has the characteristics of
metal and covalent crystals, it also has a high melting point, high hardness, excellent thermal and
chemical inertness, excellent electrical conductivity and metallic reflectivity [3]. When the film is
thin enough, it is translucent in the visible region, and has high reflectance in the infrared, can also
be used as selective solar transmission film [4]. In addition, TiN film also has high temperature
strength, excellent corrosion resistance and good thermal conductivity [5-8]. It was the first widely
used in industry and the hard-film material, the study has become a hot spot of hard layer at home
and abroad. Because of these interesting features it has attracted wide attention of researchers and
are extensively used in technological applications such as in the tool, mold, decorative materials and
integrated circuits [9].
With the depth study of TiN film, people put forward higher requirements in the uniformity,
abrasion resistance, corrosion resistance and reliability, etc. To meet this trend, many researchers
have done a lot of research on preparation and properties of TiN film [10-14]. The electronic
behaviors, the performance of lattice dynamics and thermodynamics of TiN are very important to
reveal its properties. For example, Isaev et al. [15] propounded that the superconductivity transition
metal nitrides was related with abnormalities of phonon spectrum. However, this aspects’ study was
not enough, consequently, this study is necessary. We would like to investigate he electronic
structure, Lattice Dynamics behavior (Phonon spectrum, phonon density of state, etc) and thermal

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292 Mechanical Engineering and Green Manufacturing II

properties (Gibbs free energy, thermal expansion, specific heat at constant volume, and entropy at
temperatures are calculated from the phonon frequencies on the q-point sampling mesh) of TiN film,
in doing so, We can have a deeper understanding of it.

Computational Details
For the first-principles calculations, we employed the plane-wave basis projector augmented wave
(PAW) method [16] in the framework of density-functional theory within the generalized gradient
approximation in the Perdew-Burke-Ernzerhof form [17] as implemented in the VASP (Vienna
ab-initio simulation package) code [18–20].
Phonon calculations were performed using the Parlinski-Li-Kawazoe method [21] as implemented
in the PHONOPY code. [22] For calculating the force constants in real space, we used the energy
cutoff of 400 eV, together with 2×2×2 supercells (of the primitive cell) and 5×5×5 k-mesh generated
in accordance with the Monkhorst-Pack scheme [23] for TiN. There are two ways for forces to
calculate, (1) atomic forces from finite displacements and (2) given force constants. We chose the
first one, then calculated phonon related properties: phonon dispersion relations, phonon density of
state, partial density of state. The calculated phonon dispersion confirms the dynamic stability for
TiN. Based on our phonon dispersion data, gibbs free energy, heat capacity and entropy at
temperatures are calculated by the Equation (1), (2) and (3), respectively; And thermal expansion, and
specific heat are obtained by using the quasi-harmonic approximation (QHA).
1 
ω 
F( T ) = Et ot +
2 ∫ F( ω )
ω d ω + κ T ∫ F( ω ) l n 1 − exp(

) dω
κ T 
(1)


ω 
 κ T 
ω   (2)
S( T ) = κ  ∫ F( ω )d ω − ∫ F( ω ) l n  1 − ex p( ) d ω 
 ex p(
ω )  κT  
 κT 
2

ω  
ω 
 κ T  ex p  κ T  (3)
    F( ω )d ( ω )
Cν ( T ) = κ ∫  
2

ω 
 ex p 
κ T  − 1
   

Where F(T ) , S(T ) and C(

ν
T)
are free energy, entropy and heat capacity, respectively;
, ω ,
κ and T are Planck constant, Frequency, Kelvin temperature and Boltzmann constant,

respectively; F( ω ) is phonon density of state.

A part of temperature effect can be included into total energy of electronic structure through
phonon (Helmholtz) free energy at constant volume. But what we interest is thermal properties at
constant pressure. We need some transformation from function of V to function of p. Gibbs free
energy is defined at a constant pressure by the following transformation:
G( T , P ) = U (V ) + F ( T ; V ) + PV  (4)
mi n V
 p h o n o n 
Where  f u n c t i o n ⋅ o f ⋅ V 
mi nV

implies to find unique minimum value in the brackets by changing volume. Since the volume
dependencies of energies in electronic and phonon structures are different, volume giving the
minimum value of the energy function in the square brackets shifts from the value calculated only
from electronic structure even at the temperature of 0 K. By increasing temperature, the volume
dependence of phonon free energy changes, then the equilibrium volume at temperatures changes.
This is considered as thermal expansion under this approximation. [22]
 Applied Mechanics and Materials Vols. 155-156 293

Results and Discussion

First, we optimize the lattice constants to obtain a relaxed structure. The initial lattice parameters
are taken from previous theoretical and experimental values as a starting point for geometry
optimization. The calculated lattice constant of TiN is 0.4256 nm, nearly the same to previous
theoretical and experimental values [24, 25]. Then we calculate the electronic structure, phonon
spectra and thermal properties of TiN.
A. Electronic structure
Brillouin zone for the face-centered cubic lattice is shown in Fig 1. The band structure and total
DOS projected at the different atomic sites for TiN are shown in Fig 2, respectively. The origin of the
energy scale corresponds to the Fermi level of the compound. the Fermi level for TiN has a relative
displacement of about 2 eV to the valence band direction. Close to the Fermi level, the total DOS for
TiN composed of Ti-3d and N-2p states.
The band structure calculations show that the bonding in this compound is mostly covalent. This
bonding character helps to explain the extreme hardness of this kind of materials. The band structure
calculations show that the Fermi level (EF) intersects the transition metal 3d bands. These partially
filled bands give rise to the metallic conductivity observed in this nitride. The particularly large
stability of this compound is the consequence of filled metal 3d-nitrogen 2p bonding states.
The constituents of the bands near EF have greater influences on the properties of compounds.
According to the knowledge of the group theory, the classification of energy states for each K point
can be obtained by the irreducible represent (IR) of the point group [26]. For the origin of BZ, the Γ
point, the point group of this K point is Td, so that the energy states of the Γ point is classified into
eight states according to the IR of the Td group: one nondegenerate states; four two-fold degenerate
state and three three-fold degenerate states. This is different with the result made by Li et al. [27].
Different models can cause the difference of number of the bands.
The bands crossed by EF are half occupied, thus TiN has the ability of taking part in chemical
reactions and also has the surface activity. Take some surfaces of TiN for an example, they could be
easily oxidized.

Fig. 1. Brillouin zone for the face-centered Fig. 2. The band structure and total density of
cubic lattice. state for TiN.
B.Phonons
For rock-salt type TiN, there are only two atoms in its formula unit, therefore, six phonon modes
exist in the dispersion relations. The calculated phonon dispersion curves, corresponding phonon
density of state and partial density of state are shown in Figs 3, 4 and 5, respectively. Table 1 lists the
frequency at special points with others for comparison. While our calculated dispersion for TiN is in
good agreement with other calculation [28, 29].
There is an anomalous dip in the longitudinal acoustic modes of TiN along the Γ to X direction, and
both the longitudinal and transverse acoustic modes along the Γ to X to K direction. Irregularity of
these longitudinal and transverse acoustic modes can also be observed in the Γ to L direction. Phonon
294 Mechanical Engineering and Green Manufacturing II

dispersion curves also exhibit a reverse order in LO and TO modes along the Γ to X direction. Such
anomalies in phonon frequencies can be understood with the nesting of the Fermi surface by the wave
vector (q). The calculated phonon dispersion curves do not contain soft modes at any direction, which
confirms the stability of TiN at zero pressure.
Due to large mass difference between nitrogen and transition metal Ti atoms, there exists large gap
between the acoustic branches dominated by displacements of the heavy transition metal and optical
modes involving displacements of mainly nitrogen atoms. While the main contribution to acoustic
phonons results from the transition metal sublattice, the high frequency phonons stem from the
nitrogen ions. This is expected because the nitrogen atom is lighter than the transition metal Ti atom,
which leads to comparatively weaker electron-phonon interactions. The covalent character of the
N-N bonding is also decisive for the high frequency of phonons involving the nitrogen atoms.
Interesting features of optical phonon modes are observed at Γ point. The optical phonon branches
are nearly flat at the Γ point, and this flatness of the optical modes causes a very sharp peak in the
phonon density of state.

Fig. 3. Phonon dispersion curves of TiN Fig. 4. Phonon density of state of TiN
Table 1 The phonon frequency of TiN at
special points.
Special points This work[THz] Others[THz]

(optical 15.25 14.13[28] 14.91[29]

phonon)

L(LO) 16.63 17.31[29]

L(TO) 14.82 16.46[28] 15.44[29]

L(LA) 7.63 8.44[28] 7.66[29]

L(LA) 5.77 5.69[28] 5.27[29]

Fig. 5. Phonon partial density of state of TiN
C.Thermal properties
We present a comparative theoretical analysis of thermal properties like specific heat, entropy and
free energy aiming to understand (a) the temperature dependence of the specific heat and (b) the
contribution of various phonon modes to thermal properties that will be useful in developing
statistical thermodynamical model to predict thermal properties of their superlattices.
We use phonon density of state by Eq. 1-3 to estimate the temperature dependence of the free
energy, heat capacity, and entropy of the TiN compound. The temperature-dependent variations of
the free energy, entropy and heat capacity at constant volume are plotted in Fig. 6. Due to the specific
heat at low temperature (below 300 K) is dominated by acoustic phonons and is inversely
proportional to the cube of the velocity of sound, the specific heat of TiN rises rapidly at low
temperatures. At high temperatures, the Cv values of all the material, is identical to the Dulong-Petit
value (for diatomic system). A crossover to this classical limit is set by the effective Debye
 Applied Mechanics and Materials Vols. 155-156 295

temperature. Clearly, the free energy decreases gradually with increasing temperature in the plot. It
can also be seen that the entropy change increases rapidly as the temperature increases for low
temperatures.
Using previous results of thermal properties, thermal expansion and heat capacity at constant
pressure can be calculated under the quasi-harmonic approximation. The calculated Helmholtz free
energy curves of TiN for temperature ranging from 0 up to 1000 K are shown in Fig. 7. The locus of
the equilibrium lattice parameters at different temperatures are also presented. Fig. 8 shows the
temperature dependence of the bulk modulus B and volume. Clearly, the bulk modulus B(T)
decreases and volume increases along with the increase of temperature. This kind of temperature
effect is very common for compounds and metals. The specific heat at constant volume CV can be
directly calculated through Eq. 3, while the specific heat at constant pressure CP can be evaluated by

the thermodynamic relations CP − CV = α V ( T ) B( T )T , where the isobaric thermal expansion

2

1  ∂V 
αV ( T ) =  
V  ∂T P
coefficient can be calculated according to the formula . Calculated CV and CP of
TiN at constant pressure are displayed in Fig. 9, so the difference in CV and CP gives a measure of
lattice anharmonicity. Fig. 10 demonstrate the theoretical temperature dependencies of thermal
expansion as well as the experimental data for TiN compound.

Fig.6. Heat capacity (Cv), entropy and free

energy as functions of temperature of TiN.
Indigo-blue horizontal line represents classical Fig.8. Temperatures dependence of the bulk
Dulong–Petit limit of Cv. modulus and volume for TiN.

Fig. 9. Specific heat capacities of TiN. In which

Fig.7. Dependence of the Helmholtz free Cp-polyfit at constant puressure vs temperture
energy on crystal volume at various is obtained by polynomial fittings of Cv and S;
temperatures and the locus of the minimum of and CP at constant puressure vs tempertures is
the free energy for TiN, (The Helmholtz free ∂G 2

derived by −T ∂T . 2

energy at 0 K and 100 K coincide ).

296 Mechanical Engineering and Green Manufacturing II

Fig. 10. The temperatures dependence of thermal expansion coefficient for TiN; The experimental
data obtained by Bogdanov [30], the calculated data by obtained Milevskii [31] and Wolf [32].

Summary
In conclusion, we have presented a comparative first principles theoretical analysis of electronic
structure, vibrational spectra and thermal properties of TiN. Our results are mostly in agreement
with the available experimental and theoretical findings. TiN is metal exhibiting a large gap in its
phonon spectra. Anomalies in the phonon dispersion of metallic TiN, manifested as dips in acoustic
branches, can be understood through the nesting of the Fermi surface as determined from our
calculations. The calculated phonon dispersion curves do not contain soft modes in any direction,
which confirms the stability of TiN compound. Under the QHA method, specific heat, thermal
expansion and bulk modulus at temperatures are calculated. The B(T) decreases along with the
increase of temperature. Thermodynamical results at various temperatures were considered little in
previous experiments, and these comprise the original contributions of this study.

Acknowledgments
The authors would like to thank the National Natural Science Foundation of China (Grant No.
50845065), Natural Science Foundation of Inner Mongolia (Grant No. 2009MS0812), Research
Program at Universities of Inner Mongolia Autonomous Region (Grant No. NJ10103), and
Innovation Foundation of Inner Mongolia University of Science & Technology (Grant No.
2009NC028) for financial supports.

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Mechanical Engineering and Green Manufacturing II
10.4028/www.scientific.net/AMM.155-156

Ab Initio Study of the Phonon Frequency, Electrical and Thermal Properties of TiN
10.4028/www.scientific.net/AMM.155-156.291