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1997 Thermodynamics
1997 Thermodynamics
The microstructure and electrical transport properties of immiscible copper-niobium alloy thin films
Journal of Applied Physics 103, 033511 (2008); 10.1063/1.2836970
I. INTRODUCTION
include low-temperature annealing, the experimental phase
Over the recent decades an increasing variety of non- formation ranges may approach those which are expected
equilibrium methods have been developed which allow the when metastable equilibria between amorphous and crystal-
synthesis of amorphous metallic alloys to be performed. 1–3 line solid solutions develop. Exceptions from these rules
Such methods are vapor phase deposition, melt quenching, may be observed in cases such as Nb–Cr, where the Gibbs
and, invented more recently, a number of methods which energy differences between the phases are small.6
enable the preparation of amorphous metallic alloys in the In contrast to systems with negative heats of mixing, in
solid state at relatively low temperatures. Among these latter the great majority of systems with positive heats of mixing
methods are vitrification by loading with hydrogen, solid- nonequilibrium processing results in the formation of super-
state reactions in multilayer films, mechanical alloying or saturated solid solutions rather than amorphous phases. Ex-
attrition, and particle irradiation. The tendency for amor- amples are systems which have very limited equilibrium
phous phase formation has been observed to be most pro- solid solubility and which do not form intermetallic phases,
nounced in alloy systems where the heats of mixing are such as Cu–Co, Cu–Fe, or Ag–Cu, which can nevertheless
strongly negative, hence in systems with strong tendency for be obtained as thermodynamically unstable solid solutions
compound formation. Examples are the Ti–Ni, Zr–Ni, and over wide composition ranges by mechanical alloying 7–9 as
the Zr–Co systems, in which the heats of formation of vari- well as by vapor phase deposition.10–13 Formation of solid
ous stable and metastable compounds, including the amor- solutions rather than amorphous phases in such systems is
phous phase, typically amount to several tens of kJ/g atom, 4,5 understandable from a thermodynamic viewpoint, in particu-
and in which amorphous phases can be obtained over wide lar in systems which exhibit immiscibility even in the liquid
composition ranges by most of the above mentioned meth- state. In such cases, the Gibbs energy of the amorphous
ods. This explains why investigations on amorphous phase phase, which is considered to be the low-temperature con-
formation have been carried out in the past mostly on sys- tinuation of the liquid phase, will not intersect with the
tems with negative heats of mixing. Gibbs energies of the solid solutions. Rather, the amorphous
Although the details of amorphous phase formation cer- phase will have Gibbs energies higher than the solid
tainly depend on the preparation method used, there is a solutions for all concentrations in such systems. Exceptions
general trend to correlate the phases formed and the concen- may occur in cases where the heats of mixing of the solid
tration ranges in which they occur with the thermodynamics solutions and the amorphous phases are quite different in
of the system considered.4 As the phases which compete with magnitude or even different in sign. A more sophisticated
amorphous phases are mainly the crystalline solid solu- thermodynamic ap- proach of amorphous phases would have
tions, two approaches are proposed to describe the composi- to consider the fact that amorphous phases are usually more
tion ranges of amorphous phase formation. First, the phase stable than expected from linear extrapolations of the liquid
formation ranges in cases where partitioning is completely Gibbs energies to low temperatures. 14 This stabilization of
suppressed by processing are usually given by the T 0 curves the amorphous phase originates from short-range ordering
where the Gibbs energies of amorphous and crystalline solid which develops in the liquid phase upon undercooling.
solutions intersect. Second, when the preparation conditions However, until now, this has only been investigated in
systems with negative heats of mixing in the
a)
liquid/amorphous phase.
Corresponding author. Electronic mail: carsten.michaelsen@gkss.de
Although these arguments indicate that amorphous
phases are unlikely to occur in alloy systems with positive
6024 J. Appl. Phys. 81 (9), 1 May 1997 0021-8979/97/81(9)/6024/7/$10.00 © 1997 American Institute of Physics
+ 12 kJ/g atom at 1800 °C. The positive heat of mixing in
the liquid phase is further revealed by the (eutectic or peri-
tectic) solidification temperature which is accepted in all pre-
vious investigations to be at 1080 ± 10 °C, close to the melt-
ing point of pure Cu. If the heat of mixing in the liquid phase
would be zero, or even negative, this solidification tempera-
ture would be significantly lower, and the phase diagram
would display a much more pronounced eutectic behavior.
For example, the eutectic temperature would be depressed by
approximately 200 °C if the liquid heat of mixing would be
zero. Since this is not observed, it can be deduced unambigu-
ously by a simple consideration of the phase diagram that the
liquid heat of mixing is positive. In spite of this high positive
heat of mixing, we have found the formation of amorphous
FIG. 1. Phase diagram of the Nb–Cu system, determined by the CALPHAD phases over a wide composition range to occur by sputtering.
method. The data points are taken from Refs. 24 and 25. The relatively poor In the present article, isothermal and nonisothermal DSC is
agreement between experimental and calculated liquidus curves is discussed used to characterize both the kinetics and the thermodynam-
in the appendix.
ics of amorphous Nb–Cu phases quantitatively. These data
are combined with a modeling of the thermodynamic func-
heats of mixing, there is a minor number of investigations tions of the system, thus providing deeper insight into the
that report on amorphous phase formation is systems such as thermodynamics of amorphous phase formation in an appar-
Ag–Fe,15,16 Ag–Co,17 Ag–Ni,17 Ag–Cu,11 W–Cu,18,19 and ently immiscible system.
Ta–Cu,19 some of which are immiscible even in the liquid
state. Some of these publications appear not fully convincing II. EXPERIMENT
when only diffraction methods were used to determine Alloy thin films with concentrations in the range 32–77
whether a phase was amorphous. However, additional sup- at. % Cu were deposited by triode-magnetron sputtering
port for the presence of an amorphous phase was provided in from elemental Nb (4N5) and Cu (4N) targets onto sap-
some cases by investigations of the transformation behavior phire substrates that were cooled either by flowing water or
towards equilibrium, such as differential scanning calorim- by liquid nitrogen. The base pressure prior to the deposition
etry (DSC) measurements, which showed that this transfor- was 2 × 10—9 mbar, and the sputtering was carried out in a
mation takes place in a rather narrow temperature range, a 3.7 × 10—3 mbar argon ambient (7N) at a deposition rate of
feature that is characteristic of crystallization of an amor- 1 nm/s. Each film was about 4 µm in total thickness. A row
phous phase, or characteristic of usual nucleation-and- of 16 substrates, each of 7 mm width, was positioned be-
growth processes in general. 20–22 In contrast, much broader tween the sputter sources so that a concentration gradient
transformation curves are usually found upon decomposition occurred along them which amounted to about 3 at. % per
and subsequent grain growth of supersaturated crystalline sample (‘‘composition spread’’). The compositions of the
solid solutions.7,8,23 The formation of amorphous phases in films were determined by energy-dispersive x-ray spectrom-
systems which are immiscible even in the liquid state is ex- etry in a scanning electron microscope. The structural inves-
ceptional, and is in contrast to the current understanding of tigations were performed by Cu Ka x-ray diffraction (XRD)
the thermodynamics of liquid phases. It indicates that the in symmetrical Bragg–Brentano geometry using a Siemens
Gibbs energy of the amorphous phase is much lower than D5000 powder diffractometer.
expected from the equilibrium phase diagram, and suggests Free-standing samples for the DSC experiments were
that a change of sign in the enthalpy of mixing of the liquid obtained by peeling the films from the substrates. Subse-
state may take place during cooling. quently, the films were loaded into Cu pans. The DSC mea-
In the present article we report on our investigation of surements were performed under argon atmosphere (6N) in
amorphous phase formation in the Nb–Cu system. As can be a Perkin-Elmer DSC 7. The constant-heating-rate traces were
seen in Fig. 1, the mutual solubility in the solid terminal taken at 40 °C/min and the base lines were established by
phases is negligible. The true liquidus curve is not well de- repeating the measurements under identical conditions. An
termined, and previous investigations indicated that impuri- isothermal DSC measurement was performed by heating to
ties may have major influences on the liquidus curve, so that the desired temperature at a rate of 20 °C/min, and then hold-
either a very flat liquidus curve was found, as displayed in ing the temperature until there was no further change in the
Fig. 1, or a liquid miscibility gap may be observed. How- signal.
ever, from both types of phase diagrams it can be concluded
that the Gibbs energy of mixing of the liquid phase is small
III. RESULTS
in this temperature range. This implies that enthalpy and en-
tropy just compensate each other at these temperatures, As illustrated in Fig. 2, the XRD measurements of the
hence the liquid phase enthalpy must be positive. Assuming Nb–Cu alloy films which were deposited on liquid-nitrogen-
an entropy of an ideally random solution, this allows us to cooled substrates showed diffuse halos typical of amorphous
estimate the liquid enthalpy of mixing to be about phases for all concentrations investigated (32–77 at. % Cu),
J. Appl. Phys., Vol. 81, No. 9, 1 May 1997 Michaelsen, Gente, and Bormann 602
FIG. 4. Isothermal DSC trace of a Nb54Cu46 sample at 410 °C. The solid
line was obtained by a fit of the JMA kinetic Eq. (1) to the data points.
FIG. 2. XRD patterns of Nb–Cu alloy films with various compositions,
deposited onto liquid-nitrogen-cooled substrates.
( )
the amorphous phase the pure element liquid phases were
taken as reference states. The model used for all phases was ever, in view of a lack of unambiguous experimental data for
the liquid Gibbs energy, we kept the number of coefficients
G i ( x,T ) =Giref +G idi +G xs . (A1) as small as possible and fixed Tg at 900 K (627 °C) in the
In this equation, G = xNbG (T) + xCuG (T) is the
ref 0,Nb 0,Cu present calculation. The coefficients so determined are given
in Table I.
i i i
Gibbs energy of a mechanical mixture of the elemental i
phases. Gidi in Eq. (A1) is the energy contribution due to
configurational entropy in an ideally random solution, and
Gxsi is given by
1
W. L. Johnson, Prog. Mater. Sci. 30, 81 (1986).
G ( x,T )=x Nb
xs
Cu( A+BT+C/T ) . (A2)
2
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