grenoble2015 copper electroplating parameters optimisation · of doing it within the existing bath...

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Aqueous based copper electroplating seems the most reliable, flexible, cost effective method to create a copper layer on stainless steel coupler devices; this however, doesn’t imply a straightforward application, as subcomponents geometry is complex and tolerances are tight. At CERN, two existing copper electroplating baths were tested to evaluate the feasibility of plating three couplers subcomponents within the demanded dimensional tolerances. COMSOL Multiphysics® Electrodeposition Module was used to optimise the counter electrode geometry with the objective of achieving an as even as possible copper layer thickness, as well as obtaining the plating parameters such as applied current density and plating time. Introduction Physics Metal electrodes obey to Ohm’s law: Current density vector: , with Electrolyte in excess and vigorous agitation: Current density vector: , with Electrode kinetics are not negligible, but do not induce significate electrolyte concentration variations between the bulk and the electrode surface. Electrode/Electrolyte interface: , The relation between current density and overpotential (h) can be described by the Butler-Volmer or Tafel equation, and also directly through experimental data obtained from polarisation curves. Model creation Components geometry: CEC (hollow geometry) Copper plating tolerances: 10 +/- 5 μm Surface to be plated: Internal WEC (hollow geometry) Copper plating tolerances: 10 +/- 5 μm Surface to be plated: Internal WIC (hollow geometry) Copper plating tolerances: 20 +/- 10 μm Surface to be plated: External Electrochemistry Copper sulfate plating bath: CuSO 4 .5H 2 0 75 g/l H 2 SO 4 (96%) 100 ml/l Cl (NaCl) 0.075 g/l Conductivity 22.6 S/m at 23 °C Copper sulfate plating reactions: CuCN 26 g/l NaKC 4 H 4 O 6 60 g/l Na 2 CO 3 15 g/l NaOH 12 g/l NaCN 42 g/l Conductivity 10.6 S/m at 45 °C Copper cyanide plating bath: ሺሻ ሺ௦ሻ ሺሻ ଶା ሺ௦ሻ ሺሻ ଶሺሻ ሺሻ cathodic reaction ሺሻ ଶሺሻ ሺሻ cathodic reaction anodic reaction (Ti/Pt anode) anodic reaction (Ti/Pt anode) Copper cyanide plating reactions: -200 -100 0 100 200 -2 -1 0 1 2 3 Current density (A.m -2 ) Overpotential (V) Cyanide plating bath anodic branch Cyanide plating bath cathodic branch Sulfate plating bath anodic branch Sulfate plating bath cathodic branch Copper plating baths polarisation curve Conclusions The work developed with Comsol allowed to evaluate the feasibility of plating complex geometries such as the ones of the couplers subcomponents. The data acquired from the different simulations allowed to: chose the most interesting operating bath; define, within a few iterations, an optimum working geometry for the CEC and WEC anode; define, the optimum working parameters, current density and plating time, which allows to achieve the copper layer thickness within the specified tolerances. Concerning the WIC geometry, simulation data showed that the copper sulfate plating bath wasn’t able to respect the specified copper layer thickness specifications without long plating times; on the other hand, the copper cyanide bath, was capable of doing it within the existing bath and anodes setup. Physics interface: Electrodeposition, Secondary (edsec) Results CEC with copper sulfate bath: CEC current density distribution with a non-optimised anode CEC current density distribution with an optimised anode 0 20 40 60 80 100 120 140 0 10 20 30 40 50 60 0 0.5 1 1.5 2 Plating time (min) Plated thickness (μm) Applied current density (A/dm 2 ) Minimum Maximum Copper thickness Plating time Optimum plating parameters WEC with copper sulfate bath: WEC current density distribution with an optimised anode 0 20 40 60 80 100 120 140 160 0 10 20 30 40 50 60 0 0.5 1 1.5 2 Plating time (min) Plated thickness (μm) Applied current density (A/dm 2 ) Minimum Maximum Copper thickness Plating time Optimum plating parameters WIC: 0 100 200 300 400 500 600 0 20 40 60 80 100 120 140 0 0.2 0.4 0.6 0.8 1 1.2 Plating time (min) Plated thickness (μm) Applied current density (A/dm 2 ) Minimum Maximum Copper sulfate Copper cyanide Time copper sulfate Time copper cyanide Optimum plating parameters Copper sulfate bath (green & black line) had very long plating times for the WIC geometry, thus the choice went to the copper cyanide as plating bath (orange & grey line). References 1. http://www.comsol.com/electrodeposition-module COMSOL Conference Grenoble 2015 COMSOL Conference Grenoble 2015 Excerpt from the proceedings of the 2015 COMSOL Conference in Grenoble

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Page 1: Grenoble2015 Copper Electroplating Parameters Optimisation · of doing it within the existing bath and anodes setup. Physics interface: Electrodeposition, Secondary (edsec) Results

Aqueous based copper electroplating seems the mostreliable, flexible, cost effective method to create a copperlayer on stainless steel coupler devices; this however,doesn’t imply a straightforward application, assubcomponents geometry is complex and tolerances aretight. At CERN, two existing copper electroplating bathswere tested to evaluate the feasibility of plating threecouplers subcomponents within the demanded dimensionaltolerances. COMSOL Multiphysics® ElectrodepositionModule was used to optimise the counter electrodegeometry with the objective of achieving an as even aspossible copper layer thickness, as well as obtaining theplating parameters such as applied current density andplating time.

Introduction

Physics

Metal electrodes obey to Ohm’s law:

Current density vector: , with

Electrolyte in excess and vigorous agitation:

Current density vector: , with

Electrode kinetics are not negligible, but do not induce significate electrolyte concentration variations between the

bulk and the electrode surface. Electrode/Electrolyte interface: ,

The relation between current density and overpotential (h)can be described by the Butler-Volmer or Tafel equation,and also directly through experimental data obtained frompolarisation curves.

Model creation

Components geometry:

CEC (hollow geometry)Copper plating tolerances:10 +/- 5 µm Surface to be plated: Internal

WEC (hollow geometry)Copper plating tolerances:10 +/- 5 µm Surface to be plated: Internal

WIC (hollow geometry)Copper plating tolerances:20 +/- 10 µm Surface to be plated: External

Electrochemistry

Copper sulfate plating bath:CuSO4.5H20 75 g/lH2SO4 (96%) 100 ml/lCl (NaCl) 0.075 g/lConductivity 22.6 S/m

at 23 °C

Copper sulfate plating reactions:

CuCN 26 g/lNaKC4H4O6 60 g/lNa2CO3 15 g/lNaOH 12 g/lNaCN 42 g/lConductivity 10.6 S/m

at 45 °C

Copper cyanide plating bath:

cathodic reaction

cathodic reaction

anodic reaction (Ti/Pt anode)

anodic reaction (Ti/Pt anode)

Copper cyanide plating reactions:

-200

-100

0

100

200

-2 -1 0 1 2 3

Cur

rent

den

sity

(A

.m-2

)

Overpotential (V)

Cyanide plating bath anodic branch Cyanide plating bath cathodic branch

Sulfate plating bath anodic branch Sulfate plating bath cathodic branch

Copper plating baths polarisation curve

Conclusions

The work developed with Comsol allowed to evaluate the feasibility of platingcomplex geometries such as the ones of the couplers subcomponents. Thedata acquired from the different simulations allowed to: chose the mostinteresting operating bath; define, within a few iterations, an optimum workinggeometry for the CEC and WEC anode; define, the optimum workingparameters, current density and plating time, which allows to achieve thecopper layer thickness within the specified tolerances. Concerning the WICgeometry, simulation data showed that the copper sulfate plating bath wasn’table to respect the specified copper layer thickness specifications withoutlong plating times; on the other hand, the copper cyanide bath, was capableof doing it within the existing bath and anodes setup.

Physics interface:Electrodeposition, Secondary (edsec)

Results

CEC with copper sulfate bath:

CEC current density distribution with a

non-optimised anode

CEC current density distribution with an optimised anode

0

20

40

60

80

100

120

140

0

10

20

30

40

50

60

0 0.5 1 1.5 2

Pla

ting

time

(min

)

Pla

ted

thic

knes

s (µ

m)

Applied current density (A/dm2)

Minimum MaximumCopper thickness Plating time

Optimum platingparameters

WEC with copper sulfate bath:

WEC current density distribution with an optimised anode

0

20

40

60

80

100

120

140

160

0

10

20

30

40

50

60

0 0.5 1 1.5 2

Pla

ting

time

(min

)

Pla

ted

thic

knes

s (µ

m)

Applied current density (A/dm2)

Minimum Maximum Copper thickness Plating time

Optimum platingparameters

WIC:

0

100

200

300

400

500

600

0

20

40

60

80

100

120

140

0 0.2 0.4 0.6 0.8 1 1.2

Pla

ting

time

(min

)

Pla

ted

thic

knes

s (µ

m)

Applied current density (A/dm2)

Minimum Maximum Copper sulfate

Copper cyanide Time copper sulfate Time copper cyanide

Optimum platingparameters

Copper sulfate bath (green & black line) had very longplating times for the WIC geometry, thus the choice went tothe copper cyanide as plating bath (orange & grey line).

References

1. http://www.comsol.com/electrodeposition-module

COMSOLConferenceGrenoble 2015

COMSOLConferenceGrenoble 2015

Excerpt from the proceedings of the 2015 COMSOL Conference in Grenoble