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Determining the diffusion coefficient of Ni in

Cu from a Ni/Cu thin film using linear heating,
scanning Auger microscopy and a numerical
solution of Fick's second law

Article in Surface and Interface Analysis · June 2010

DOI: 10.1002/sia.3377

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Heinrich Joubert Jacobus Terblans

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Retrieved on: 08 September 2016
Research Article
Received: 27 August 2009 Revised: 18 February 2010 Accepted: 3 March 2010 Published online in Wiley Interscience: 11 May 2010

(www.interscience.wiley.com) DOI 10.1002/sia.3377

Determining the diffusion coefficient of Ni

in Cu from a Ni/Cu thin film using linear
heating, scanning Auger microscopy and a
numerical solution of Fick’s second law†
H. D. Joubert, J. J. Terblans∗ and H. C. Swart
In previous studies, linear temperature ramping was used to determine diffusion coefficients from bulk-to-surface segregation
experiments of a low concentration solute. Thin film diffusion studies usually employ a classical heating regime, where a
sample’s annealing time is taken as the time between insertion and removal from a furnace. The aforementioned study type
assumes that the time it takes to heat up a sample after insertion is instantaneous, while the sample cools down instantaneously
after removal from the furnace. This assumption is incorrect, as it does not compensate for the various mechanisms that govern
heat transfer. In order to eliminate the uncertainty, a linear ramping regime is used and samples were annealed inside an ultra
high vacuum (UHV) environment with a programmed linear heating scheme. After each anneal, a depth profile was obtained
by simultaneously bombarding the sample with Ar+ ions and monitoring the exposed surface with an electron beam which
excites Auger electrons, among others. The depth profiles were normalised and the time scale converted to depth. In order to
compare the diffusion profiles obtained from classical annealing studies to the linearly ramped studies, the diffusion coefficient
obtained for a classical study of Ni diffusing in Cu was inserted into a numerical solution of Fick’s second law, modified to
include linear temperature ramping. A diffusion coefficient was also obtained from linearly ramped samples. Comparison of the
diffusion profiles calculated with the diffusion coefficients obtained from classical heating and linear heating showed a large
discrepancy between the profiles. Copyright
c 2010 John Wiley & Sons, Ltd.

Keywords: diffusion; thin films; linear temperature ramping; Mixing–Roughness–Information model

Introduction ting three parameters to a measured diffusion profile:[4] (i) Atomic

Ni/Cu thin films are of great importance in the microelectronics
industry where thin film couples form an integral part in
semiconductor chips.[1] Diffusion coefficients provide an insight
into how much mixing between the elements of a thin film couple
takes place after a certain time and at an elevated temperature,[2]
similar to the conditions experienced by semiconductor chips
during its lifetime. The inherent problem with diffusion parameters
available in literature for Ni/Cu thin films is the variation in the
structure and composition of the thin film couple.[3] The difference
in microstructures results in diffusion parameters that have a very
wide range of values, as indicated in Table 1. Of further concern
is the annealing methods used in certain studies of thin film
diffusion couples,[2] where the time of annealing is taken as the
time between insertion of a sample into the furnace and removal
of the sample from the furnace (classical heating), ignoring the
mechanisms that govern heat transfer.[2]
Classical thin film diffusion studies rely on annealing of many
samples for different times and at different temperatures. Inter-
face broadening results from such a heat treatment and analysis of
this broadening yields the diffusion coefficient for the system be-
ing investigated. Superimposed on the diffusion-induced profile
broadening is the broadening that results from the analysis tech-
nique used to probe the sample, known as the depth resolution.[4]
One popular model that describes a depth resolution function
is the Mixing–Roughness–Information (MRI) model.[5] The MRI
mixing width, (ii) information depth and (iii) the surface/interface
roughness. The MRI model has proved its efficacy over the years
and has the added advantage of extracting diffusion coefficients
(D) from experimental data using the relation[5]
2Dt =
σ 2 (1)
where t is the annealing time and
σ 2 is the change in the interface
roughness between the reference sample and a particular sample
subjected to annealing.
As mentioned previously, most diffusion studies rely on a
constant, well-defined annealing time which ignores heat transfer
mechanisms. The MRI model is no different in this respect. In
this study, a linear heating scheme for binary thin film diffusion
couples described in Ref. [2] was expanded to bypass the effect
that heat transfer mechanisms have on classical heat treatments,
by using a programmed heat treatment that involves linearly
ramping and cooling a sample under ultra high vacuum (UHV)
∗ Correspondence to: J. J. Terblans, Department of Physics, University of the
Free State, PO Box 339, ZA-9300 Bloemfontein, Republic of South Africa.
E-mail: TerblansJJ@ufs.ac.za
† Paper published as part of the ECASIA 2009 special issue.
1213

Department of Physics, University of the Free State, PO Box 339, ZA-9300

model attempts to describe the depth resolution function by fit- Bloemfontein, Republic of South Africa

Surf. Interface Anal. 2010, 42, 1213–1216 Copyright

c 2010 John Wiley & Sons, Ltd.

Table 1. Diffusion parameters obtained in the present work and from
literature
References D0 (m2 s−1 ) Q (kJ mol−1 )
Present study 7.06 × 10−13 87.7
[1] 2.6 × 10−10 133.1
[3] 4.9 × 10−13 103.2
[6] 6.48 × 10−9±1 130.5 ± 13
[8] 2 × 10−5 228.7
[9] 6.93 × 10−7 90.4
[10] 1.4 × 10−14 106.1
Figure 1. Representation of the change in the diffusion coefficient during
a temperature ramp.
conditions. The diffusion coefficient was then obtained from
the ramped sample data, which is Ni/Cu in this study. The
drawback in using temperature ramping for diffusion studies
is that the diffusion coefficient is not constant during the heat
treatment. One can numerically solve Fick’s second law[2] and
incorporate linear ramping into the numerical calculation. The
constants of diffusion are determined from the calculations.
A recursive calculation scheme is required to obtain the pre-
exponential factor and activation energy, but this process is
a very time consuming method as the numerical solution of
Fick’s second law is a time intensive process. In order to speed
up the analysis of the linear ramped sample data, the profiles
were analyzed with the MRI model using a diffusion-coefficient-
weighted temperature to simulate a perfect classical annealing
scheme in which the temperature of the sample does increase
and decrease instantaneously after insertion and removal from a
furnace. In other words, the linear ramp heat treatment equated
to a perfect classical heat treatment.
The perfect classical annealing scheme is the preferred method
of analysis as the classical annealing approach employs a direct
error function solution of Fick’s second law. The difficulty in
reconciling the two different methods arises from the varying
diffusion coefficient that is found when ramping the temperature
of a sample. An example of the varying diffusion coefficient is
shown in Fig. 1, which was constructed by calculating the diffusion
coefficient at each point during the temperature ramp using the
diffusion parameters listed in Ref. [6].
If one assumes that the energy transferred to a sample in a
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perfect classical heat treatment is the same as in a linearly ramped
www.interscience.wiley.com/journal/sia Copyright

c 2010 John Wiley & Sons, Ltd.
H. D. Joubert, J. J. Terblans and H. C. Swart
Figure 2. Comparison of diffusion profiles calculated from linear ramping
and perfect classical heating.
heat treatment, then diffusion profiles obtained by the two heating
methods should also be the same.
The energy transferred to the ramped sample can be repre-
sented by the area underneath the curve shown in Fig. 1. If one
now uses a weighted temperature obtained from the area un-
der the curve (also shown in Fig. 1), a perfect classical diffusion
calculation can be performed with the weighted temperature by
simply changing the annealing time until the area underneath the
perfect classical curve matches the area underneath the ramped
curve. The amount of energy transferred to a sample during a
perfect classical anneal will then equal the energy transferred to
the sample during a linear ramp anneal, and hence the diffusion
profiles will be the same for the two different annealing methods.
This hypothesis was confirmed by performing a linear ramp
diffusion calculation and comparing it to a perfect classical
diffusion calculation performed with the weighted annealing
temperature, with the perfect classical calculation accurately
following the linear ramp calculation, shown in Fig. 2. Using
the method described above, one can analyze ramped diffusion
profiles with the well-established MRI model and extract diffusion
parameters from the ramped data. A detailed description of the
MRI model is given in Ref. [7] and the method of determining the
diffusion parameters is given in Ref. [5].
Experimental
Physical vapor deposition was employed to deposit Cu/Ni thin
films onto a passivated silicon (100) substrate. The nickel film had
a thickness of 1000 Å, whereas the copper film had a thickness
of 6000 Å. Evaporation was performed in a vacuum with a base
pressure of <10−6 Torr.
Auger electron spectroscopy combined with Ar+ ion bombard-
ment was used to obtain depth profiles of the Ni/Cu samples. The
Ar+ ion beam was set at 2 keV Ar++ , whereas the primary elec-
tron beam was set at 5 keV. Linear ramping was performed with a
custom heater inside the Auger apparatus. A Chromel/Alumel ther-
mocouple measured the temperature at the back of the sample
while the heater’s temperature was computer controlled. Samples
were heated at 0.3 ◦ C s−1 and cooled at −0.1 ◦ C s−1 to maximum
temperatures ranging from 350 to 500 ◦ C.
Surf. Interface Anal. 2010, 42, 1213–1216
Diffusion coefficient of Ni in Cu from a linearly ramped Ni/Cu thin film
Figure 3. Example of four linear ramp temperature profiles used in the
study.
Figure 4. Experimental data and MRI fit for sample linearly ramped to
a maximum temperature of 400 ◦ C at a heating rate of 0.3 ◦ C s−1 and
a cooling rate of −0.1 ◦ C s−1 . The MRI parameters are also shown in
the figure, with λ the information depth, w the mixing width and σ the
surface/interface roughness.
Results and Discussion
Four linear temperature ramp profiles used in this study are shown
in Fig. 3 (375 ◦ C was omitted for clarity). The effects of the heat
treatments on the diffusion profile of a Ni/Cu thin film are shown
in Fig. 4 where the sample was linearly ramped to a maximum of
400 ◦ C, repeated five times. For clarity, only the reference profile
along with profiles measured after two and five ramps are shown
in Fig. 4. From the MRI fit parameters obtained from equation (1),
an Arrhenius graph was constructed and is shown in Figure 5.
From the regression line the diffusion parameters were obtained
and are listed in Table 1. To aid the comparison of the diffusion
parameters obtained in this work with the parameters of other
authors, an Arrhenius plot is constructed from the data in Table 1
and is shown in Fig. 6.
The diffusion parameters obtained in this study are significantly
smaller than the diffusion parameters obtained by applying the
MRI model to a classical heat treatment. This implies that the
classical analysis employed in Ref. [6] yielded diffusion parameters
that overestimated the rate of diffusion. A comparison between a
Surf. Interface Anal. 2010, 42, 1213–1216 Copyright

c 2010 John Wiley & Sons, Ltd.
Figure 5. Arrhenius graph constructed from the MRI fit parameters.
Temperature values are the diffusion weighted temperatures.
Figure 6. Arrhenius plot of the diffusion parameters listed in Table 1.
diffusion profile calculated with classical and linear ramp diffusion
parameters is shown in Fig. 7 to illustrate this point. The diffusion
profile calculated using classically obtained diffusion parameters
predicts more diffusion than the linearly ramped profile. This
correlates well with the results obtained in Ref. [2], highlighting
the importance of controlling the heat treatment that is used
during diffusion studies.
Conclusion
The effect of annealing method on the diffusion parameters
extracted from thin film diffusion experiments was analyzed.
Several samples were subjected to a controlled heat treatment
that involved linear heating and cooling in an UHV environment.
To analyze the samples that underwent linear ramping, a perfect
classical heat treatment was proposed. The MRI model, in
conjunction with the proposed perfect classical heating method,
was used to determine the diffusion parameters of Ni in Cu.
These parameters were smaller than the parameters obtained
in another study conducted by the authors which employed
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classical annealing of Ni/Cu thin films. The results indicate
www.interscience.wiley.com/journal/sia
 H. D. Joubert, J. J. Terblans and H. C. Swart

Acknowledgements
The authors would like to thank the National Research Foundation
for financial assistance for this study and the staff of the Physics
department of the University of the Free State for many informative
discussions. Special thanks to Mr Adriaan Hugo for his tireless
maintenance of the experimental apparatus.

References
Figure 7. Comparison of the diffusion profiles calculated with diffusion
parameters obtained from a classical heat treatment and a linear ramp
heat treatment.
an overestimation of diffusion when using the classical heat
treatment. Since the preparation conditions of the samples
analyzed (linearly ramped and classically annealed) are the same,
only the annealing method will result in different diffusion
parameters being extracted from the measured depth profiles.
One can therefore conclude that the method of annealing plays an
important part when attempting to extract diffusion parameters.
1216
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[4] S. Hofmann, Thin Solid Films 2001, 398–399, 336.
[5] J. Y. Wang, A. Zalar, Y. H. Zhao, E. J. Mittemeijer, Thin Solid Films
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[6] H. D. Joubert, J. J. Terblans, H. C. Swart, Proceedings of the 2009
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[7] S. Hoffman, Surf. Interface Anal. 1994, 21, 673.
[8] T. Vandijk, E. J. Mittemeijer, Thin Solid Films 1977, 41, 173.
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c 2010 John Wiley & Sons, Ltd. Surf. Interface Anal. 2010, 42, 1213–1216