Numerical and experimental validation of electrochemical

migration
Name: Ali Dayoub Neptun Code: AS6FCO
Course: Numerical Methods in Electronics Technology Process Modeling
Abstract:
Numerical modeling aims to simulate physical phenomena to provide a
comprehensive understanding of them in order to ensure accurate
interpretation. This report aims to review the existing “Numerical simulation of
electrochemical migration” model and provide new suggestions for its
development.
Basically, the numerical modeling of the electrochemical migration model is
based on representing the features of the phenomenon using mathematical
equations with the aim of calculating the characteristic parameters of the
process, the most important of which is MTTF.

Tools:
Numerical verification using mathematical tools (MATLAB).
Experimental verification of the model using (water drop (WD) test).

Content:
1- Flowchart of the studied numerical model
2- Analysis of the studied model:
a. Dissolution of metal at the anode
b. Modeling the transfer of ions through the electrolyte from the
anode to the cathode
c. Reduction at cathode
d. The final numerical form of the Nernst-Planck equation (ion
transport equation)
e. MATLAB software

f. Additional information about the studied numerical model

3- Limitations of the studied model and suggestions for expansion

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1- Flowchart of the studied numerical model:

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 2- Analysis of the studied model:
The model is two-dimensional (x and y directions), but it has only a single
thickness parameter towards the third direction (z).
The Poisson equation was used to calculate the voltage distribution between
two electrodes:[3]

Based on the hypothesis of the bioelectric neutrality of the medium (quantum

neutrality of the medium, i.e. no accumulation of charge in the medium, and in
other words, the medium does not contain currents or charges), it is:
Net electric charge density per unit volume : ρ = 0.
Thus, Poisson's equation turns into Laplace's equation and Equation (1)
becomes:[4]

Calculating the electric field based on the voltage distribution:

Water oxidation occurs at the contact boundaries between the anode and the
electrolyte on the one hand and between the cathode and the electrolyte on
the other hand.[5,6]

Oxidation effect at the anode: Dissolution of metal at the anode into ions.
Oxidation effect at the cathode: Formation of hydrogen gas and reduction of
metal ions.
Assuming that oxidation is ideal, i.e. there is always enough e - to achieve
Equation 4 at the anode (melting the metal) and Equation 6 at the cathode
(reduction of ions).

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 a. Dissolution of metal at the anode:

The dissolution of the metal at the anode is calculated according to the anode
removal rate, which is driven by the reaction current density at the anode.
Therefore, the change in metal at the anode (the rate of dissolution of the metal
as a function of time) is:[7,8]

Assuming uniformity with the electric field, the melting begins evenly along the
anode.
M, F, S have a fixed values.
σ depends on:

1-Slightly affects the amount of metal ions (Cu2+ ions) present in the solution
due to ionic conduction.
2-To a lesser extent, the formation of hydrogen is affected by the hopping of
protons.
The second factor (hydrogen formation) was neglected because its effect is
much less than the effect of the first factor (Cu2+ ions).[9]

Thus σ is given as a function of the metal concentration:[10]

b. Modeling the transfer of ions through the electrolyte from the

anode to the cathode:
When modeling ion transfer processes using the Nernst-Planck equation, the
Butler-Volmer equations or the Nernst equation are used as boundary
conditions for Cu 2 + ion concentration, which take into account the
dependence of the surface concentration of electroactive ions on:
(1)the electrode potential
(2)and/or current density.
In the studied model, the surface concentration of electroactive ions was not
calculable.
So a “theoretical” maximum ion concentration of Cu 2 + at the anode ( cmax ) has
been set to 7.56 ×10 −5 g/l at 20 °C.

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(The experimental results showed that this assumption worked well) Further
dissolution of Cu was not possible over cmax .

The right side of the equation contains three terms:[11,12]

1-The first relates to the diffusion constant D
2-The second relates to the speed of spread.
3-The third relates to the strength of the electric field and the concentration of
ions.
About diffusion constant D:
The diffusion constant can be calculated according to the Einstein diffusion
relationship:[13]

K, z, e have a fixed values.

About speed of diffusion v:
It is assumed that the speed of diffusion is negligible (v=0), i.e. there is no
convective movement in the system.
the 2D vectorial form of Eq. (9) is the following:

c. Reduction at cathode:
Ions in the cathode are reduced, and there are two types of reduction:
(1)dendrite formation.
(2)precipitation.
The ions either form direct dendrites or they form various complexes, such as
metal hydroxides, which dissolve and precipitate when the concentration of
metal ions becomes saturated.

Randomness in cathode reduction processes:

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 1- Randomness in determining the region from which the growth of
dendrites begins:
The possibility of dendrite growth exists in every cell connected to the cathode,
but it occurs in certain locations of the cathode, and these locations cannot be
determined by the model, as the model assumed quantization of the system
because it cannot describe each ion alone, but rather thousands of ions as a
complete unit that behave in the same way.

2- Randomness in choosing dendrites or precipitate:

The model adopted randomness (a random threshold) in choosing whether the

ions would be reduced directly into dendrites or into complexes that would
subsequently precipitate.[14]
In both cases, the reduction depends on the number of ions, and therefore the
reduction possibilities are linked to the Cu 2+ ion concentration in the solution.

Thus, the probability of formation of dendrites in Equation (13) in the cell

connected to cathode n is compared with this random threshold th. If the
probability of formation of dendrites in cell n is greater than the random
threshold in step k, then Cu2+ ions are reduced and dendrites are formed.
If the probability of dendrite formation in cell n is smaller or equal to the
random threshold in step k, then Cu 2+ ions are not reduced. The move is made
to step k+1.
The model justifies the use of equations (12) and (13) by saying that they can
be proven experimentally.

d. The final numerical form of the Nernst-Planck equation (ion

transport equation):
Eq (9)→ Eq(11) → Eq(14)
The numerical conversion of the previously defined partial dif- ferential
equations was done by the Finite Difference Method (FDM) and was solved by
an explicit Forward Time Central Space (FTCS) algorithm[15]. The FDM-FTCS

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numerical format of Nernst-Plank equation ( Eq. (11) , which contains first- and
second-order derivatives as well) is the following:

According to Eq 14, the FDM-FTCS format of the rest of the applied partial
differential equations Eq. (1) and (2) can be generated.

e. MATLAB software:
The calculated surface was 200 ×200 μm 2 .
The gap size between the copper conductor wires was 200 μm,
the bias voltage was 10 VDC,
the temperature was 20 °C,
and the water droplet was 15 μl deionzed water (contaminant-free).
The grid dependency analyses resulted in optimal cell size at 1 μm (x, y), which
meant 40.0 0 0 cells.
Towards the z -direction, the thickness was also 1 μm.
The time step was chosen to 175 μs according to the Courant–Friedrichs–Lewy
(CFL) condition. (The time step depends on the velocity of the dendrite
formation, which was known from the experimental tests.)
The boundary conditions of the model are summarized in Table 1 .

The boundary condition for the number of ions at the anode (ion concentration)
in step k is equal to their number in the previous step k-1 plus the amount of
anodic dissolution (i.e. the amount that dissolved) Δc.
The boundary conditions for the number of ions at the cathode in step k are
equal to their number in the previous cell cath-1 in the previous step k-1.

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 f. Additional information about the studied numerical model:
1- The boundary condition at the cathode side (the previous value of the
neighbouring cells) ensures the zero mass outflux of the Cu 2 + ions
there. However, in accordance with the law of conservation of charge in
the approximation of the electroneutrality of the medium and without
taking into account the double electri- cal layers, the current passing
through the anode must be equal to the current passing through the
cathode. This contradiction is re- solved with the assumption that the
copper ions which reach the cathode realize the electrical conduction.
(The fluxes are assumed to be 0 through the other two insulating walls
of the system).
2- On the cathode side, there are two conditions of the reduction, first is
that the reducing ion need to be able the join to the cathode, and the
second is that the given cell has not already filled with Cu.
3- The reduction of the Cu 2 + ions at the cathode (the dendrite formation)
reduces the distance between the anode and the cath- ode. This changes
the electric field and the potential distribution, so Eq. (1) and 2 needs to
be recalculated after each reduction step.
4- The ability of the numerical model was validated by experimental WD
tests.
5- Parallel copper wires were fabricated by conventional subtractive printed
wiring board technology.
6- Altogether, 20 WD tests were done to investigate the MTTF. The results
of the models were validated with the measurement results.
7- The microstructure of the dendrites was studied by an Olympus BX50
optical microscope and by a FEI Inspect S50 Scanning Electron Mi-
croscope (SEM).

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 3- Limitations of the studied model and suggestions for expansion:
3-1- Incubation period of the process
MTTF consists of an incubation period and a period of dendrite growth.

Studied model:
The model assumed the omission of the formation of a water layer on the
substrate (incubation period of the process) by absorption of water molecules
or condensation of water.

Suggested model:
Conduct a detailed study or analysis of the potential effects of omitting the
water layer on the substrate in the model. and provide an accurate assessment
of the expected impacts and changes to MTTF and overall system performance.

3-2- Model dimensions:

Literature Reviews:
Kwok and Wu [4] developed a one-dimensional numerical model of the
electrochemical diffusion migration process.
Covering the transport mechanism in a binary electrolyte solution, they found
that modeling the reaction kinetics at electrodes requires special treatment of
boundary conditions.
He and Li [7] developed the 2D lattice Boltzmann model (LBM) to study
electrochemical processes.
The model is capable of simulating ionic transport processes and covers:
Migration due to electric field
Diffusion due to concentration gradient
Convection due to fluid flow.
They demonstrated the model's capabilities through a variety of
electrochemical problems, ranging from diffusion-dominated convection to
migration-dominated primary and secondary current distributions.
Studied model:

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2D numerical model. This means that the model has full resolution on the
surface (x and y directions), but only one thickness parameter towards the third
direction (z).
Suggested model:
It can be better to use a 3D model that takes into account all three directions (x,
y and z) to achieve higher accuracy in analysis and prediction, assuming the
thickness of dendrites as an important variable.

3-3- Assume that oxidation is ideal, i.e. there is always enough e- to achieve
dissolution at the anode.

3-4- Assuming the presence of uniformity in the electric field, therefore melting
begins evenly along the positive electrode (anode):
The anode dissolution process can be naturally heterogeneous, as specific areas
of the anode can be affected more than others, resulting in uneven corrosion
along the anode.

Measures can be taken to achieve greater uniformity in the dissolution process.

For example, a condition can be added at the anode to provide even distribution
of current across the anode, to reduce uneven corrosion.
Other procedures include controlling the process temperature and flow of fluids
used in the electrolytic cell, and this can also affect the uniformity of the melting
process.

3-5-The water droplet was 15 μl deionized water (contaminant-free)

Simulation and modeling can be modified based on the specific type and
concentration of pollutant.
the model can be extended e.g.,
Heavy metal contamination: We can add certain concentrations of heavy
metals such as lead or mercury to a drop of water, which may affect the
electrochemical migration process or disrupt the flow of ions in the solution.
Organic chemical contaminants: such as volatile organic solvents, which can
affect electrochemical migration by changing the reactive properties of the
stationary phase or interfering with the chemical reactions involved.

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Oil pollution: We can add a specific percentage of mineral oil to a drop of water
and monitor its effect on the water surface, its ability to evaporate, and its effect
on the process

3-6- Randomness in choosing the threshold.

Restricting the randomness of the choice between deposition and dendrites by
specifying a specific value to compare with the cost function (probabilistic
relationship in the model).

3-7- Randomness in choosing the sites from which the growth of dendrites
begins.
Restricting randomness to a specific cost function by developing the
experimentally imposed probability relationship or by creating a new cost
function that links the algorithm to the design parameters.

3-8- The formation of hydrogen is not taken into account in the conductivity σ,
although it has some effect on the conductivity of the solution through the
hopping of protons.
3-9- In the model, the surface concentration was not calculable, so the
maximum concentration value (cmax) was set at which melting occurs, and no
melting occurs at a value higher than cmax.
3-10- No convective movement in the system is assumed and hence speed of
propagation v = 0.
3-11- The movement of copper ions in the solution was studied, but the
movement of other ions in it was not studied.

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