Materials Science and Engineering A 424 (2006) 128–137

On the spinodal nature of the phase segregation and formation

of stable nanostructure in the Ti–Si–N system
R.F. Zhang a , S. Veprek b,∗
aDepartment of Materials Science and Engineering, Tsinghua University, 100084 Beijing, China
b Department of Chemistry, Technical University of Munich, Lichtenbergstr. 4, D-85747 Munich, Germany
Received 1 April 2005; received in revised form 1 November 2005; accepted 1 March 2006

Abstract
The free energy of the mixed Ti–Si–N system is calculated according to a semi-empirical thermodynamic formula based on the sub-lattice
model for different activities of nitrogen. The results show that the phase segregation in the ternary Ti–Si–N systems is of chemically spinodal
nature at a nitrogen pressure and deposition temperature typically used for the deposition of the superhard nc-TiN/a-Si3 N4 nanocomposites, i.e.
pN2 ≥ 10−3 mbar and Tdep 550–600 ◦ C, respectively. Only at much lower nitrogen pressure and much higher temperature, can the chemically
spinodal decomposition be restrained. A simple estimate of the interfacial strain energy for a semi-coherent interface, as expected for this system,
shows that this contribution is unlikely to hinder the system being also coherently spinodal. It is further shown that kinetic constraints, such as
Tdep ≤ 300 ◦ C and low pN2 , although within the range where the stoichiometric nitrides should be fully spinodally segregated, will kinetically hinder
the system to reach the thermodynamically driven equilibrium.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Spinodal nature; Phase segregation; Ti–Si–N system

1. Introduction by about one monolayer of X-ray amorphous silicon nitride (see

Section 4.1 in [6]). This segregation occurs provided the nitro-
The generic design concept for the preparation of super- gen pressure and deposition temperature are high enough, as
hard nanocomposites with a high thermal stability and oxidation explained in earlier papers [1,2]:
resistance is based on a strong, thermodynamically driven phase
segregation in a binary (or ternary) system, that results in the
- When deposited under the conditions of a sufficiently high
formation of a nanostructure with “compositional modulation”
nitrogen pressure (0.3–1 mbar) that provides the thermo-
with a sharp and strong interface [1,2]. In their original paper [1],
dynamic driving force and sufficiently high temperature
Veprek and Reiprich omitted using the term “spinodal” because
(≥550 ◦ C) that assures the diffusion rate-controlled phase
of lack of unambiguous evidence, and because in some publi-
segregation to be completed during the deposition [1], the
cations, where the hardening of mixed transition metal nitrides
crystallite size is fairly uniform [7].
and carbides upon annealing was attributed to spinodal decom-
- The morphology, as observed by transmission electron
position, such evidence was absent. The term “spinodal” was not
microscopy for nanocomposites deposited by plasma-induced
even mentioned in the references quoted in those papers [3–5].
chemical vapor deposition (P-CVD) under conditions that
Meanwhile, experimental results were obtained that support the
favor the formation of fully segregated, thermally very sta-
spinodal nature of the segregation of the TiN and Si3 N4 phases
ble nanostructure, is typical of spinodally segregated systems
during the deposition of the nc-TiN/a-Si3 N4 nanocomposites,
with a high de-mixing enthalpy [6].
consisting of 3–4 nm small TiN nanocrystals “glued” together
- In systems that display a larger misfit between the phases,
such as nc-TiN/a-BN, the “optimum” crystallite size, where
∗ Corresponding author. Tel.: +49 89 289 136 24;
the TiN nanocrystals are covered with about one monolayer
fax: +49 89 289 136 26. of BN and hardness reaches a maximum, is larger than in the
E-mail address: veprek@ch.tum.de (S. Veprek). case of nc-TiN/a-Si3 N4 where this misfit is smaller [6].

0921-5093/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2006.03.017
 R.F. Zhang, S. Veprek / Materials Science and Engineering A 424 (2006) 128–137
- Coatings that were not deposited under the optimum condi-
tions, so that the phase segregation was not completed during
the deposition, show an increase in hardness upon annealing
to ≥700 ◦ C. This is accompanied by the “adjustment” of the
crystallite size to the “optimum” value of about 3–4 nm that
can be larger or smaller than the original crystallite size in the
as deposited coatings [8].
Although these findings cannot be considered as final, unam-
biguous evidence, for the spinodal nature of the phase segrega-
tion during the formation of the nanostructure in the nc-TiN/a-
Si3 N4 nanocomposites (see, e.g. [9–11] and references therein),
they provide strong support for this concept. Strong evidence of
the spinodal nature can be provided by thermodynamic calcula-
tions of the Gibbs free energy of the mixed phases as a function
of their relative fraction which yields the “chemical spinodal”
curve (i.e. the second derivative of the Gibbs free energy of the
mixed system is negative) for the TiN/Si3 N4 system consisting
of immiscible, stoichiometric nitrides (see Section 3).
Because the spinodal nature of the phase segregation upon
the deposition of the superhard nc-TiN/a-Si3 N4 and similar
nanocomposites was questioned by some workers recently [12],
we shall briefly summarize in the next section the thermody-
namic conditions needed for spinodal phase segregation to occur.
After presenting the calculations that yield the evidence for
chemical spinodal in this system under the conditions outlined in
[1,2,13,14], we shall discuss possible effects of the strain energy
in this system in order to show that it is unlikely to hinder the
TiN–Si3 N4 system to decompose spinodally. Section 4 will deal
with a brief discussion of kinetic conditions that are needed
in this system to reach that equilibrium. Two conditions will
be identified and briefly discussed: (a) a sufficiently high tem-
perature that is needed to allow the diffusion-controlled phase
segregation to be completed during the deposition and (b) a suf-
ficiently high nitrogen pressure that is needed to provide the
necessary flux of chemisorbed nitrogen to form stoichiomet-
ric nitrides at a given deposition rate. The paper will end with
conclusions and outlook for the possibilities of the design of
superhard nanocomposites with a high thermal stability [1,2] in
other, advanced systems.
2. On the nature of spinodal decomposition
In his studies of the stability of phases, Gibbs distinguished
between phase transformations that are “large in degree but small
in extent” and those which are “small in degree and large in
extent”. Nowadays, the former ones are called “nucleation and
growth”, whereas the spinodal phase segregation is typical of
the latter.
The term “spinodal” was introduced by van der Waals in
order to describe that part of the binodal line D–E–F–G–H in
his isotherm between the inflection points E and G (see Fig. 1)
where the second derivative of pressure with respect to volume is
negative [15]. The part of the isotherm between G and C is usu-
ally assigned as physically unrealistic because there exist three
different values of volume for a given pressure, and because of
the apparently negative compressibility between points F and D
129
(see, e.g. [16], p. 19). In equilibrium, this is the regime of coexis-
tence of gaseous and liquid phases. Thus, the curve C–D–E–F–G
is replaced by a straight line between points G and C so that the
areas C–D–E and E–F–G are equal (the so called “Maxwell
construction”).
Obviously, in its original definition by van der Waals, the
spinodal phase separation (“decomposition”) does not exclude
nucleation but it refers only to thermodynamic instability. The
negative value of the second derivative means that the system
between E and G is inherently unstable with respect to infinitesi-
mal fluctuations, i.e. the phase segregation proceeds without any
activation, or, in other terms, the activation energy is zero or of
the order of the thermal energy kT. Nevertheless, the thermody-
namically unstable region between E and G is experimentally
accessible either by a fast overheating of a liquid that suppresses
boiling (E → F) or a fast compression of a clean vapor (G → F)
as used in the Wilson’s cloud chamber to monitor charged parti-
cles ([16], p. 149). Already this example shows that the approach
of a system towards equilibrium within the spinodal region is
controlled by both the thermodynamics and kinetics of the phase
segregation. For more recent discussion of the theoretical aspects
of the spinodal decomposition we refer to [10,11].
Nucleation and growth are not explicitly excluded during the
spinodal phase segregation because, under appropriate condi-
tions, the activation energy for the formation of the new phase
approaches zero. This can be illustrated by the example of the
isotherms plotted for different temperatures below and above
the critical point as illustrated in Fig. 1b for CO2 . When cooling
the CO2 gas from a higher temperature to the critical point of
T = 31.04 ◦ C, the distinction between the gas and liquid phase
vanishes and, upon a further infinitesimal cooling, the phase sep-
aration occurs without activation, and the fraction of the liquid
continuously increases. The situation is somewhat more com-
plex but physically not different in solid solutions whenever the
given system displays the coherency spinodal (see below).
Since the original work of van der Waals, spinodal decompo-
sition has been studied in a variety of systems [10,11] including
oxide [9] and metallic [17,18] glasses, in polymers [19,20], in
adsorbates on surfaces [21,22] and in metallic alloys [23–25].
Fig. 1c shows examples of the dependence of the Gibbs free
energy of the mixed system A1−x Bx on the composition for the
case of partial miscibility (upper curve) and total immiscibility
(lower curve). If the second derivative of the Gibbs free energy
of the mixed phase
G0f with the composition x is negative,
δ2 G0f (x)
<0 (1)
δx2
the system meets the conditions of being “chemically” spinodal,
i.e. inherently unstable to infinitesimal fluctuations of the com-
position in its initial stage of decomposition. Thus, the phase
segregation occurs spontaneously without any activation. This
is the case in the whole range of the composition for the lower
curve, but only within the concentration x1 < x < x2 for the upper
one. Within the range x < x < x1 and x2 < x < x of the upper
curve, an infinitesimal fluctuation results in an increase of the
free energy. The system there is metastable, and the segrega-
130 R.F. Zhang, S. Veprek / Materials Science and Engineering A 424 (2006) 128–137

Fig. 1. (a) van der Waals isotherm showing the “spinodal” part of the curve between the inflection points E and G. (b) Isotherms of CO2 for temperature below and
above the critical point. (c) Schematics of the Gibbs free energy of the formation of mixed phases of the nitrides (e.g. TiN + Si3 N4 ) vs. the composition for a high
(T2 ) and lower (T1 ) temperature. A similar dependence is expected (and found, see below) for a low and a high nitrogen pressure at the same temperature.

tion occurs by nucleation and growth with activation energy of is determined by the balance between the decrease of
G0f
nucleation Eact > 0 [10,11]. due to de-mixing (Fig. 1c), the compositional gradient term
The theoretical basis of spinodal decomposition in solid 2K(
x)2 /2λ2 and the strain energy term η2 E Vm (
x)2 [31]. K
alloys was developed by Cahn and Hillard [26–30]. They consid- in the compositional gradient term is proportionality constant
ered the modification of the chemical spinodal shown in Fig. 1c depending on the difference in the bond energies of like and
by the contribution of the compositional gradient and elastic unlike atom pairs. In the strain energy term, η = (da/dx)/a is
strain energy of the de-mixing phase that represents a desta- the fractional change of lattice parameter per unit composition
bilizing term in the total free energy. For the initial stage of change, E = EY /(1 − ν), where EY and ν are the Young’s modu-
spinodal decomposition characterized by a compositional vari- lus and Poisson’s ratio, respectively, and Vm is the molar volume.
ation x0 ±
x with a modulation period λ, the total free energy This term represents the destabilizing contribution of the strain
that “drives” the spinodal decomposition energy resulting from the mismatch between the phases formed

 upon de-mixing.
d2
G0f 2K 2  (
x)2
G= + + 2η E V m (2) The theory of Hillert and Cahn describes only the initial stage
dx2 λ2 2 of the spinodal decomposition in which a certain “characteristic”
 R.F. Zhang, S. Veprek / Materials Science and Engineering A 424 (2006) 128–137
period of the compositional modulation grows faster than any
other Fourier component. The larger the interfacial (mismatch)
energy, the larger the period. When this contribution is large as
compared with the chemical term
G0f , the spinodal decomposi-
tion will be hindered. For a coherent interface (i.e. without misfit
dislocations) the interfacial strain energy is ≤200 mJ/m2 and it
can be as low as 1 mJ/m2 reported for the Cu–Si alloy ([31],
p. 144). For a semi-coherent interface, this energy may reach a
value of up to about 500 mJ/m2 , and for incoherent interfaces
up to 1000 mJ/m2 ([31], p. 147).
The thermodynamic calculations of the chemical spinodal
can be performed relatively simply for systems that form mixed
crystals. The heat of de-mixing,
H > 0, can be measured by
differential scanning calorimetry (DSC). For metallic alloys, the
enthalpy of de-mixing is relatively low: about 2 kJ/mol for Au–Pt
[32], 10.8 kJ/mol for Cu–Fe [33] and 33 kJ/mol for Cu–W sys-
tem [34]. In transition metal systems, the largest (“de-mixing”)
heat of formation of 65 kJ/mol was reported for Ag–W [35]. Rel-
atively low values of the heat of de-mixing were reported also
for the Co2 TiO4 –CoAl2 O4 system [36]. With a typical peri-
odicity of the spinodally decomposed systems of the order of
5–10 nm (see, e.g. [36]) and corresponding specific interface
area of the order of 104 –103 m2 /mol (depending also on the
morphology) it is clear that spinodal decomposition in such sys-
tems can occur only if the final phases are coherent. A much
higher free energy of de-mixing is needed if the final phases are
either semi-coherent or incoherent, like, e.g. in the Ti–Si–N sys-
tem and many oxide glasses. Nevertheless, if the free energy of
the de-mixing is of the order of ≥100 kJ/mol, spinodal decom-
position is possible also in systems that form incoherent phases
provided the activation energy of the nucleation, which occurs
only in the later stages of the spinodally initiated decomposition,
is sufficiently low.
In the case of stoichiometric transition metal nitride (TiN,
Wn N, VN, etc.) in combination with a covalent nitride (Si3 N4 ,
BN, AlN) which is immiscible [37], the calculations of the chem-
ical spinodal are difficult. Moreover, the majority of papers
that dealt with spinodal decomposition in solid alloys did not
need to consider the activity of a gaseous phase. However, a
simple consideration of the thermodynamics of the system, as
presented already in [1] and more recently with more details in
[13],
 y  x   y 
xTiN + x · Si3 N4 = xTiSiy + + 2x · N2
3 2 3
(3)
clearly shows that, at a given temperature, the chemical equilib-
rium shifts to the right hand side of reaction (3) when the pressure
of nitrogen decreases. Under vacuum and a high temperature, the
nitrides are unstable and miscible phases will form. For exam-
ple, the saturation pressure of nitrogen over Si3 N4 reaches 1 atm
at a temperature of 2151 K [38]. Consequently, the miscibility
of such systems depends on both the temperature and nitrogen
pressure which has to be accounted for when discussing the
possible spinodal nature of such phase segregation.
In the Ti–Si–N system, the mutual solubility increases with
increasing temperature and decreasing nitrogen pressure as illus-
131
trated schematically by the upper curve in Fig. 1c. Therefore,
the formation of the superhard nc-TiN/a-Si3 N4 nanocomposite
with a high thermal stability requires a sufficiently high nitrogen
pressure during the deposition. This was emphasized in [1,2] and
discussed in more detail recently [13]. Such general behavior of
nitride systems is illustrated, among many other examples, by
the Inx Ga1−x Ny As1−y system where the “spinodal temperature”
(i.e. the onset of spinodal de-mixing) increases with increasing
nitrogen pressure [39].
The decomposition of metastable, aluminum-rich solid solu-
tion fcc-(Ti1−x Alx )N into the stable fcc-TiN and h-AlN phases
occurs via a surface-initiated, spinodal decomposition into fcc-
TiN and c-AlN as an intermediate, followed by the c-AlN
to h-AlN transition and concomitant decrease of the hard-
ness [40,41]. The effect of nitrogen activity was not studied
in these papers. Recently it was shown that about one mono-
layer thin interfacial layer of Si3 N4 in the nc-(Ti1−x Alx )N/a-
Si3 N4 superhard nanocomposites can avoid the decomposi-
tion of fcc-(Ti1−x Alx )N up to a high temperature of 1200 ◦ C
[8]. These examples illustrate that the question of the spin-
odal nature of phase segregation in the superhard nanocompos-
ites, such as nc-TiN/a-Si3 N4 , must be verified in much detail
considering the activity of nitrogen as well as the interfacial
effects.
3. Calculation of the chemical spinodal
3.1. The basis of thermodynamic model
In a standard substitutional solution A1−x Bx , all lattice sites
are considered equivalent. Thus, the solution is formed from a
pure substance A by substituting a part of the atoms A with B.
The Gibbs free energy Gm of the mixed phase is then given by
a standard formula [42]:
  
Gm = xi · 0 Gi + RT xi · ln xi + xi · xj Iij (4)
i j>i
The first term describes the contribution of the pure substances,
the second one is the mixing entropy and the third one is the
contribution due to the interaction between the components. In
the case of a simple binary system shown in Fig. 1c, there are
only two elements A and B with corresponding fractions xA and
xB = (1 − xA ). Iij is the interaction parameter that depends on
the mutual affinity of the components. It can be attractive (i.e.
negative) when the system forms a stable solution or repulsive
when it decomposes.
This simple treatment is limited to crystalline phases that
form substitutional solution, i.e. mixed crystals. The major-
ity of solid systems have different kinds of crystal lattices
sites. They can be described by means of two or more sub-
lattices, as first proposed by Hillert and Staffansson in 1970
[43]. This is a simplified model in the sense that it assumes
random mixing within each sub-lattice, neglecting the possible
changes of the interaction parameter with the composition. In
spite of that, this model was widely and successfully used for
the calculation of the phase equilibria of interstitial solid solu-
132 R.F. Zhang, S. Veprek / Materials Science and Engineering A 424 (2006) 128–137
tions and ternary line compounds (see, e.g. [43,42], pp. 141,
487 ff).1
For example, a ternary line compound (A,B)a Cc can be con-
sidered as a continuous solid solution composed of two line com-
pounds Aa Cc and Ba Cc . Thus, in the ternary phase (A,B)a Cc , a
and c give the numbers of different sites per formula unit. The
ternary phase can be treated as a binary substitutional phase, also
called a “quasi-binary” or “pseudo-binary”. The simplest model
for such a solution can be obtained by assuming random mix-
ing of the atoms within each sub-lattice. It is then convenient
to define mole fractions for each sub-lattice. They are called
site fractions and are denoted y. The site fractions are used to
define the frame of reference for the Gibbs energy of the solution
phase. For the present ternary phase (A,B)a Cc , the Gibbs energy
is given by Eq. (5) [44].
G(A,B)a Cc = yA 0 GAa Cc + yB 0 GBa Cc
+ aRT (yA ln yA + yB ln yB ) + ayA yB IAB (5)
where a gives the numbers of sites of (A, B) sub-lattice per
formula unit. The contents of the pure elements A, B and C
are represented by their fractions xA , xB and xC (notice that
xA + xB + xC = 1). Accordingly, the site fraction of elements A
and B in the sub-lattice (A, B) can be calculated as yA = xA /
(xA + xB ) and yB = xB /(xA + xB ), respectively, whereas in the sub-
lattice C, yC = 1 is constant.
3.2. Modification and application of the model to the
TiN–Si3 N4 system
For the quasi-binary TiN–Si3 N4 systems, the line compound
(Ti,Si)N with a structure ␺ can be regarded as a continuous solid
solution phase composed of a given fraction of the stoichiometric
␺-TiN and ␺-Si3 N4 phases with the same structure ␺. Thus,
the molar Gibbs free energy of the ␺-(Ti,Si)N phase can be
expressed by,
␺ ␺ ␺ one monolayer thin Si3 N4 forms a semi-coherent interface to
G(Ti,Si)N = yTi 0 GTiN + ySi 0 GSiN4/3
+ RT (yTi ln yTi + ySi ln ySi ) + yTi ySi ITiSi:N
1 monolayer of Si3 N4 sandwiched between few nanometer thick
␺ ␺
= yTi 0 GTiN + ySi 0 GSi3 N4
3 hesion energy of such sandwich is larger than that of bulk Si3 N4
+ RT (yTi ln yTi + ySi ln ySi ) + yTi ySi ITiSi:N (6)
␺ ␺
where 0 GTiN and 0 GSi3 N4 represent the reference state of Gibbs
free energy of ␺-TiN and ␺-Si3 N4 phases. ITiSi:N is the inter-
action parameter in the ␺-(Ti,Si)N phase. Its physical meaning
is somewhat different from the interaction parameter IAB in Eq.
(5), because here ITiSi:N represents the interaction between the
nitrides. If we define x as the fraction of the component Si3 N4 in
the pseudo-binary (TiN)1−x –(Si3 N4 )x system, the site fraction
of elements Ti and Si in the sub-lattice (Ti, Si) can be calculated
as yTi = (1 − x)/((1 − x) + 3x) and ySi = 3x/((1 − x) + 3x), respec-
tively. The molar Gibbs free energy of ␺-(Ti,Si)N phase can be
1 Ternary “line compounds” are represented by a line in the compositional
triangle (see [42], p. 141).
expressed by,
␺ 1−x 0 ␺ x 0 ␺
G(Ti,Si)N = G + G
1 + 2x TiN 1 + 2x Si3 N4

1−x 1−x 3x 3x
+ RT ln + ln
1 + 2x 1 + 2x 1 + 2x 1 + 2x
3x(1 − x)
+ ITiSi:N (7)
(1 + 2x)2
The Gibbs free energies of the ␺-TiN and ␺-Si3 N4 phases can-
not be obtained directly from the published literature, because
the stoichiometric nitrides are immiscible and, therefore, the
mixed phases cannot be prepared under equilibrium conditions.
Only during plasma physical vapor deposition under conditions
far from equilibrium, such as vacuum arc evaporation [45] or
reactive sputtering [46], mixed cubic phases of (Ti–Al–Si–N)
and (Ti–Si–N), respectively, were reported. Later on, Vaz et
al. have shown that such cubic mixed Ti–Si–N phase is indeed
metastable and transforms into the cubic TiN and X-ray amor-
phous SiNx upon annealing [47]. More recently, Flink et al.
[48] investigated the mixed cubic phase Ti1−x Six N deposited by
means of vacuum arc evaporation. Kinetic limitations together
with ion bombardment-induced collisional mixing were pro-
posed to be responsible for the formation of this metastable
cubic phase which, upon annealing to 1100 ◦ C, decomposed
into a cubic TiN and SiNx . Band structure calculations per-
formed using a full potential linear muffin tin orbital method
showed that, for a given NaCl-structure, a phase separation into
cubic SiN and TiN phases is energetically more favorable than
a Ti1−x Six N solid solution [48]. Already in their first paper on
the deposition of the nc-TiN/a-Si3 N4 nanocomposites, Veprek
and Reiprich argued that one monolayer thin Si3 N4 , where the
nc-TiN/a-Si3 N4 nanocomposites reach the maximum hardness,
provides the structural flexibility to accommodate the interfa-
cial strain [1]. More recently these researchers have shown that
TiN [6]. Hao et al. have shown by means of very detailed
first-principle density functional theory calculations that one
TiN slabs represents the most stable configuration, and the deco-
[49]. Using the deposition by reactive magnetron sputtering
Söderberg et al. [50,51] and Hu et al. [52] stabilized sub-
nanometer thick layers of cubic SiN in TiN/SiNx heterostruc-
tures by epitaxial growth.
These results show that, during the deposition by means of
non-equilibrium techniques, such as plasma CVD and PVD,
an initially mixed, cubic Ti–Si–N phase decomposes into sto-
ichiometric TiN and Si3 N4 by diffusion and surface-initiated,
heteroepitaxial growth of a monolayer thin Si3 N4 on the sur-
face of stoichiometric TiN, provided a sufficiently high pressure
of nitrogen, which provides the thermodynamic driving force,
and deposition temperature of ≥550 ◦ C, which assures a suffi-
ciently fast diffusion, have been chosen during the deposition as
explained already in [1] and extended in the follow-up papers
(e.g. [2,6,13,14]). The activation energy for a “nucleation” of the
 R.F. Zhang, S. Veprek / Materials Science and Engineering A 424 (2006) 128–137 133

Si3 N4 heteroepitaxial interface is expected to be low because, The enthalpies
H0 of TiSi, TiN and Si3 N4 were taken from
as shown by Hao et al. [49], the one monolayer Si3 N4 interface the compiled thermodynamic data by Barin [53]. For a regular
in this system is more stable than bulk Si3 N4 . solution model, the enthalpy of formation can be expressed as
Unfortunately, none of the above quoted papers reports ther-
modynamic values of the mixed cubic “Ti–Si–N” phase. The
HTiSi:N
0
= ITiSi:N
0
· xSi:N · xTi:N (11)
only mixed phase, which is documented in the literature under
With the value of
HTiSi:N
0 obtained from Eq. (10), the interac-
equilibrium conditions, is Ti5 Si3 Ny used here for the calculation
of the interaction parameter. Therefore, for the present case, we tion parameter ITiSi:N between TiN–SiN4/3 can be approximately
0

approximate these values by those of pure substances, i.e. of calculated from Eq. (11),
c-TiN phase with fcc structure and h-Si3 N4 phase with hcp struc-
HTiSi:N
0
ture, respectively. This is a reasonable approximation because ITiSi:N
0
= (12)
xSi:N · xTi:N
the absolute values of the Gibbs free energy of formation of
refractory nitrides are orders of magnitude higher than those of where xSi:N and xTi:N are the fractions of the components Si
structural phase transitions. The corresponding values of Gibbs and Ti in quasi-binary TiN–Si3 N4 system. For the composition
free energies can be found in Barin’s book [53]. Thus, Eq. (7) xSi:N = xTi:N = 0.5, the interaction parameter has approximately
can be replaced by, the value of 1907 kJ/mol.
It should be emphasized that this calculation method for the
1 − x 0 fcc x 0 hex
G␺m = G + G enthalpy of the formation of mixed ternary “(Ti,Si)N” directly
1 + 2x TiN 1 + 2x Si3 N4 from the binary TiSi compound and of the interaction parameter

1−x 1−x 3x 3x is of a phenomenological nature and, therefore, approximate. In
+ RT ln + ln future, more accurate values should be calculated by ab initio, or
1 + 2x 1 + 2x 1 + 2x 1 + 2x
another first-principle method. However, as will become appar-
3x(1 − x)
+ ITiSi:N (8) ent from the results below, more accurate calculations will not
(1 + 2x)2 change the fact that the phase segregation in this system is of
spinodal nature. This is due to the fact that the Gibbs free energy
As already mentioned above and discussed elsewhere of de-mixing is much larger in this system than in the metallic
[1,2,6,13,54–57], the activity of nitrogen is an important fac- alloys, and, as discussed above, the thin Si3 N4 layer forms a
tor influencing the Gibbs free energy of the “(TiSi)N” mixed heteroepitaxial interface with TiN.
phase in the pseudo-binary (TiN)1−x –(Si3 N4 )x system. For rel- Given the fact that the ternary compound Ti5 Si3 Ny can coex-
atively low pressures discussed here, the nitrogen activity can ist with TiNx and TiSi at a nitrogen pressure of 10−8.96 atm
be expressed by incorporating the nitrogen pressure into the (1 atm = 1.01 × 105 Pa) and a temperature of 1273 K [58], one
interaction parameter ITiSi:N , because the nitrogen content in can assume that the ternary compound Ti5 Si3 Ny has the same
the “(TiSi)N” phase is directly determined by its partial pres- Gibbs free energy as the sum of TiNx and TiSi. This is similar
sure in the gas phase. Accordingly, the interaction parameters to the equilibrium of the two-phase region condition adopted
ITiSi:N at nitrogen pressure pN2 can be approximately expressed by Hillert (see [42], p. 466). In addition, the elemental com-
by, position of the compound Ti5 Si3 N4 is comparable to the sto-
ichiometry where the maximum of the hardness as function
ITiSi:N ∼
= ITiSi:N
0
+ αRT ln pN2 (9) of silicon content was obtained in the nc-TiN/a-Si3 N4 [1] and
other systems studied [6,13,57,59]. Accordingly, the parame-
where ITiSi:N
0 is the interaction parameter in the “(Ti,Si)N” phase ter α can be calculated from the mass equilibrium equation
at standard atmospheric pressure of 1 atm, and α is an adjustable 2TiNx=y/2 + 3TiSi = Ti5 Si3 Ny at temperature 1273 K and nitro-
parameter, whose value can be determined from experimental gen pressure 10−8.96 atm and from Eq. (13),
data as shown below.
␺
2GTiNx + 3GTiSi = 5G(TiSi)N = GTi5 Si3 Ny (13)
3.3. Results
(For details see Table 1, line 6 in [58] and notice the stoi-
chiometry given there for the coexistence of the phases TiSi,
The pure, stoichiometric nitrides fcc-TiN and hcp-Si3 N4 will ␺
Ti5 Si3 Ny and TiNx with x = 0.969 ≈ 1.) The value of G(TiSi)N
be regarded as the reference. The enthalpy of formation of
␺
“(Ti,Si)N”,
HTiSi:N
0 , at a composition of TiN:SiN4/3 = 1:1, can calculated from Eq. (13) equals to the Gm in the general Eq. (8)
be approximately calculated as from which the value of the interaction parameter for the com-
pound Ti5 Si3 Ny , ITiSi:N , can be calculated using a computer, and

HSi
0
3 N4
inserted into the left hand side of Eq. (9). Then, all values in Eq.

HTiSi:N
0
=
HTiSi
0
−
HTiN
0
− (9) are known except for α, which can now be calculated to be
3
 equal to 7.024.
778433
= −129704 − −346, 890 − J/mol With these values of ITiSi:N
0 and α, the Gibbs free energy dia-
3 gram of the mixed ternary phase “Ti–Si–N” can be constructed
= 476.7 kJ/mol (10) using Eqs. (8) and (9). The results for five different nitrogen
134 R.F. Zhang, S. Veprek / Materials Science and Engineering A 424 (2006) 128–137
Fig. 2. Gibbs free energy of the formation of mixed TiN + Si3 N4 system at tem-
perature of 873 K (corresponding to the upper limit of the deposition temperature
used) for five different pressures of nitrogen used in the experimental work.
pressures of 0.01, 0.001, 0.0001, 0.00001 and 0.000002 atm at
temperature 873 K are shown in Fig. 2. The temperature of 873 K
corresponds to the upper limit of deposition temperatures found
to be necessary in order to complete the TiN and Si3 N4 phase
segregation and formation of the stable, superhard nanostructure
during deposition by means of plasma CVD [1] and PVD [14].
The nitrogen pressure of 0.000002 atm (ca. 0.002 mbar) is the
lower limit of nitrogen pressure at which superhard nanocom-
posites with hardness of 52 GPa and high thermal stability could
be deposited by means of reactive magnetron sputtering [14].
If we adopt the stoichiometric nitrides TiN and Si3 N4 as the
reference state, the dependence of the Gibbs free energy on the
composition can be, for the same conditions, represented by
Fig. 3.
From Figs. 2 and 3 it can be clearly seen that for the typi-
cal conditions used during deposition by Veprek and co-workers
for plasma CVD [1] and PVD [14], the Gibbs free energy of the
mixed stoichiometric system is typical of chemical spinodal, i.e.
(δ2 G0f (x))/(δx2 ) < 0, within the whole range of compositions. It
Fig. 3. Gibbs free energy of the formation of mixed TiN + Si3 N4 system at tem-
perature of 873 K (corresponding to the upper limit of the deposition temperature
used) for five different pressures of nitrogen used in the experimental work with
stoichiometric TiN and Si3 N4 chosen as reference states.
Fig. 4. Gibbs free energy of the mixed phases calculated for very low nitrogen
pressures (see text).
is important to note that, for the optimum composition of about
8–9 at.% of Si, where the maximum hardness is achieved in
this system [1,6,13], the excess Gibbs free energy of the mixed
stoichiometric system is still more than 200 kJ/mol. This is
much larger than the expected strain energy of the semi-coherent
TiN/Si3 N4 interface (see above) because the Si atoms, coordi-
nated to nitrogen only, fit the nitrogen-terminated TiN surface
fairly well with only a relatively small tensile mismatch [6].
In order to estimate the critical pressure which may restrain
the chemical spinodal decomposition, we performed the calcu-
lations for much lower nitrogen pressures of 10−16 , 10−17.4 and
10−18 atm. The corresponding values of the Gibbs free energy
of the mixed phases are shown in Fig. 4. Obviously, the nitro-
gen pressure of 10−17.4 atm is close to the critical value for the
chemical spinodal. Therefore, the corresponding curve is shown
on expanded Gf -scale in Fig. 5. One notices the similarity of this
curve with the upper one shown in Fig. 1c. The local minima at a
low (see ‘i’ in Fig. 5) and high (see ‘ii’ in Fig. 5) Si3 N4 fraction
are due to the decrease of the enthalpy of the mixed phase by
the mixing entropy term (see Eq. (4)).
Fig. 5. Gibbs free energy calculated for nitrogen pressure of 10−17.4 atm which
is close to the critical one for chemical spinodal.
 R.F. Zhang, S. Veprek / Materials Science and Engineering A 424 (2006) 128–137
From Figs. 4 and 5 it can be clearly seen that at nitrogen pres-
sures of 10−17.4 atm, the Gibbs free energy is the critical value
for the chemical spinodal decomposition. This means that when
the nitrogen pressure is lower than 10−17.4 atm, the chemical
spinodal decomposition is depressed, while at a higher pressure
the shape of the curve is typical of chemical spinodal (see Fig. 4).
Of course, this example should be considered only as an illustra-
tive one because more exact calculations may somewhat change
the exact value of the “critical pressure”. Notice however that
the equilibrium constant of reaction (3) reaches the value of 1 at
temperature of 800 K and nitrogen pressure of about 10−16 atm
(see Fig. 4a in [13]), which is the critical pressure calculated
for the chemical spinodal here. Therefore, even a more accurate
calculation will not change the dependence shown in Fig. 5 in
principle, but only slightly modify the exact value of the critical
nitrogen pressure.
4. Discussion
Based on the sub-lattice model, the method used here for
the calculation of the Gibbs free energy of the mixed “(TiSi)N”
state, together with the simple interaction parameter, is of lim-
ited accuracy. Nevertheless, the results presented in Figs. 2 and 3
show clearly that the phase segregation in the nc-TiN/a-Si3 N4
system is of spinodal nature, because, even for a semi-coherent
interface with energy of <0.5 kJ/m2 and crystallite size of
3–5 nm (as observed by experiment), the destabilizing con-
tribution of the strain energy of several kJ/mol is orders of
magnitude smaller than the excess Gibbs free energy of the
chemical spinodal at a pressure of >10−4 atm, as typically used
in the plasma CVD deposition of superhard nanocomposites
[1]. This condition is also satisfied for deposition by means
of reactive magnetron sputtering in pure nitrogen at a pressure
of 0.002 mbar (about 2 × 10−6 atm) as reported by Prochazka
et al. [14]. In that work, a hardness of 52 GPa was achieved
in the nc-TiN/a-Si3 N4 system, and it remained stable after
annealing up to 1200 ◦ C. Even with the limited accuracy of
the present calculations, the critical nitrogen pressure for the
coherency spinodal at 873 K must be much lower than the nitro-
gen pressure of about ≥10−4 mbar (about 10−7 atm) used by
some workers, because at the low pressure of 10−16 atm the
chemical spinodal still shows an excess of Gibbs free energy
larger than that expected for the coherency strain energy (see
Fig. 4). This is in reasonable agreement with the recent calcu-
lations of the chemical equilibria in this system which show
that, at a nitrogen pressure of 10−7 atm, the equilibrium of
the system (Eq. (2)) is on the side of stoichiometric, immis-
cible nitrides also at a much higher temperature of 1000 K
[13].
Also of interest is the finding that the calculated critical pres-
sure of 10−17.4 atm is smaller than the saturation pressure of
Si3 N4 of about 10−11 atm at the temperature of 873 K [38].
Notice that because of the higher stability of TiN its saturation
pressure is lower than that of Si3 N4 [38]. Thus, the presently
used simple model gives an underestimate of the excess Gibbs
free energy of the mixed phase. This further supports the con-
clusion that also accounting for the energy of the semi-coherent
135
interface will not significantly change the coherency spinodal
curve.
For these reasons, the lack of success in reproducible deposi-
tion of superhard nanocomposites, as reported by several groups
and recently discussed in [13], is expected to be due either to
impurities [13,60] or to kinetic constraints. As mentioned in
Section 1, the kinetic constraints can be of two different origins:
(a) A too low temperature than that needed to allow the
diffusion-controlled phase segregation to be completed dur-
ing deposition [1].
(b) A too low nitrogen pressure than that needed to provide the
sufficient flux of chemisorbed nitrogen during deposition in
order to form stoichiometric nitrides at a given deposition
rate.
The first case was briefly discussed in [13] where it was shown
that the time needed for the grain boundary diffusion of, e.g. Si
within TiN over a distance of 5 nm is of the order of few 100 s
at the deposition temperature of 550 ◦ C reported in [1]. In com-
parison, several 1000 s are needed at a deposition temperature
of ≤300 ◦ C and many hours at room temperature. Obviously,
spinodal phase segregation is completed during the deposition
at 550 ◦ C, whereas it remains incomplete at about 300 ◦ C and
fully absent at room temperature.
Another possible reason for the lack of the reproducibility
can be a too low pressure, which results in a too low sticking
rate ΦS of chemisorbed nitrogen on the surface of the growing
film givenby Eq. (14),

1
ΦS = s nvth (14)
4
than that needed for the formation of stoichiometric nitrides dur-
ing the deposition. (In Eq. (14) s is the sticking coefficient, n the
concentration of nitrogen in the gas phase at the given pressure
and vth is the thermal velocity.) As the incoming N2 molecules
have to find neighboring vacancies at the surface of the grow-
ing film in order to dissociate, the sticking coefficient, which is
much less than 1 already on clean surfaces, decreases signifi-
cantly with increasing surface coverage and approaches 0 for a
full coverage [61,62]. For example, the sticking coefficient of N2
on polycrystalline W decreases to zero for a coverage approach-
ing 1 × 1015 N-atoms/cm2 [63]. A similar effect applies for low
energy (<200 eV) N2 ions (which are dominant in a nitrogen
glow discharge) because, upon approach to the metallic surface,
they are neutralized before collision with the surface. It is well
known that the reflection coefficient R of low energy ions is
high, i.e. their adsorption and implantation probability is low
[64]. Therefore, the incoming flux of N2 (and N2 + ions) towards
the surface of the growing film must be at least three to four
orders of magnitude larger than the sticking flux of Ti and Si
atoms which can be estimated from the observed growth rate.
For the deposition of superhard nanocomposites with a high
purity, which is another important factor influencing the hard-
ness (see [13,60] and references therein), deposition rates of
about 1–2 nm/s are needed [13,14]. This corresponds to a flux
136 R.F. Zhang, S. Veprek / Materials Science and Engineering A 424 (2006) 128–137
of about (4–6) × 1015 Ti and Si atoms/s cm2 . Accordingly, the
corresponding flux of nitrogen hitting the surface of the grow-
ing film must be in the range of 1018 –1019 N2 -molecules/s cm2 ,
which implies a nitrogen pressure of 10−3 to 10−2 mbar (about
10−6 to 10−5 atm). In many papers on the plasma PVD deposi-
tions of these coatings, a lower nitrogen pressure was used and
a negative bias was applied to the substrates. The low nitrogen
pressure together with the ion bombardment-induced collisional
mixing is the likely reason for incomplete segregation of the sto-
ichiometric nitrides.
This example shows that the kinetics imposes more stringent
requirements on the partial pressure of nitrogen than the ther-
modynamics.
Finally, let us discuss the possible kinetics of the segregation
“Ti–Si–N → nc-TiN + Si3 N4 (15)
and of the “stabilizing” effect of the SiNx interface. The main
argument against the spinodal nature was that the poorly defined,
mixed “Ti–Si–N” phase has – upon the phase segregation to TiN
and Si3 N4 – undergone the crystallization of TiN. We are not
aware of any reliable values of the activation energy of the recrys-
tallization of pure amorphous TiN. However, it is known that TiN
grows crystalline even when deposited at low temperatures of
<100 ◦ C. Furthermore, the recent papers discussed above clearly
show that the metastable, cubic mixed Ti–Si–N phase forms
under conditions remote from equilibrium and it decomposes
into a cubic TiN and Si3 N4 if the latter interfacial layer is suffi-
ciently thin. Therefore, at deposition temperatures of ≥550 ◦ C,
which is needed for fast phase segregation, crystallization will
never kinetically hinder the formation of the nc-TiN/a-Si3 N4 ,
where the monolayer of Si3 N4 grows almost heteroepitaxially
on the surfaces of TiN nanocrystals [6].
The high decohesion strength of the “SiNx ” interlayer (note,
the assignment “Si3 N4 ” was introduced on the basis of the mea-
sured Si 2p binding energy in these nanocomposites which cor-
responds to that of stoichiometric Si3 N4 [1]) is further supported
by the recent work of Söderberg et al. who succeeded in deposit-
ing heterostructures consisting of TiN with “SiNx ” in between.
A maximum hardness of about 33 GPa was achieved when the
thickness of the “SiNx ” interlayer was close to one monolayer
[50,51], in agreement with results of Veprek and co-workers
for the nc-TiN/a-Si3 N4 nanocomposites [1,56]. Similar results
were also recently published by Hu et al. [52]. The somewhat
broader dependence of hardness as a function of Si3 N4 interlayer
thickness with a maximum at about two monolayers of Si3 N4
reported by Hu et al., as compared with the data of Söderberg et
al., is due, most probably, to the lower quality of the multilayers
with rougher interfaces deposited by these researchers as seen
by a comparison of the transmission electron micrographs and
the low-angle XRD data reported in these papers. A rough inter-
face may also explain why some researchers find the maximum
hardness of the nc-TiN/a-Si3 N4 nanocomposites to appear at a
higher Si-content than that corresponding to one monolayer of
stoichiometric Si3 N4 .
Last but not least, these results are further supported by first-
principle theoretical calculations of Hao et al. who have shown
that the value of the decohesion energy of a “sandwich” con-
sisting of one monolayer of silicon nitride inserted between
nitrogen-terminated surfaces of TiN crystals lies between the
ideal decohesion energy of [1 1 1] and [1 1 0] TiN lattice planes
and is higher than that of bulk Si3 N4 [49]. Therefore, the tensile
strength of such a “sandwich” corresponds to the ideal deco-
hesion strength of strong, flaw-free materials. This result lends
further support to the recently reported high tensile strength of
the superhard nanocomposites, measured by means of indenta-
tion and calculated on the basis of Hertzian theory, which indeed
approached the ideal strength of such materials [65,66].
5. Conclusions and outlook
- Thermodynamic calculations of the Gibbs free energy of a
mixed system of stoichiometric TiN and Si3 N4 show that
under the deposition temperature and nitrogen pressure used
by Veprek et al. for the deposition of superhard nc-TiN/a-
Si3 N4 nanocomposites with a high thermal stability, the phase
segregation is of a spinodal nature.
- The requirement of a sufficiently high nitrogen pressure is dic-
tated mainly by the kinetics of the chemisorption of nitrogen
atoms on the surface of the growing film.
- More accurate calculations have to account for the dependence
of the interaction parameter on the composition (i.e. TiN to
Si3 N4 ratio), nitrogen partial pressure and temperature. Only
when such calculations are available, will a deeper insight into
the nature of the spinodal phase segregation in this and similar
systems be possible.
- Due to the large value of the Gibbs free energy of de-mixing
in the calculated chemical spinodal and the semi-coherent
nature of the TiN/Si3 N4 interface, the results obtained in this
paper confirm that, under the deposition conditions used by
Veprek et al., the phase segregation and formation of the super-
hard nanostructure with a high thermal stability is of spinodal
nature.
The results presented in this paper allow us to assess the pos-
sibility if in other, similar nc-Men N/a-Si3 N4 systems (Me = V,
W, etc.) the phase segregation and formation of stable, strong
nanostructure by spinodal mechanism is to be expected. Because
of the large immiscibility of many hard transition metal nitrides
with Si3 N4 and, because of the experimentally found similar
dependence of the maximum hardness at about one monolayer
coverage (see [6,57] and references therein) we expect that future
thermodynamic calculations will confirm the spinodal nature in
all these systems, as well as in nc-TiN/a-BN, although the BN
interfacial layer is not semi-coherent in this case [6]. The reason
for our prediction is the, in contrast to metallic alloys, very large
de-mixing energy, of the order of 100 kJ/mol, in these nitride
systems.
Acknowledgments
We would like to thank Professor B.X. Liu for encourage-
ment, valuable discussion and support of this work, and to
Professor Magnus Oden, Professor Catherine Stampfl and Dr.
 R.F. Zhang, S. Veprek / Materials Science and Engineering A 424 (2006) 128–137
Shiqiang Hao for providing us with their results prior to publi-
cation. Partial financial support by the National Natural Science
Foundation of China, by The Ministry of Science and Tech-
nology of China (through a Grant No. G20000627-07), by the
Tsinghua University and by the European Commission within
the 6th Framework Programme under Contract No. AST 3-CT-
2003-502741—“MACHERENA” and Contract No. COOP-CT-
2004-507839—“RESTOOL” is acknowledged.
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