Cyanide Free Acidic Thiourea

Electrolyte for Gold

Electrodeposition
M. Rea, L. Vonella, A. Vicenzo
M. Bestetti and P.L. Cavallotti
Dipartimento Chimica, Materiali e Ingegneria Chimica
Politecnico di Milano
Joint Meeting of the Physical Chemistry and Electrochemistry
Divisions of the Italian Chemical Society
XXXII Italian Meeting of Physical Chemistry
G.E.I. 2002
Introduction
Gold in Electronics
ECD films
Bonding wire
Sputter targets
Gold Properties
Contact Resistance
Resistivity
Corrosion Resistance
Wear Resistance
contacts, connectors, solderable films on PCB
conductor tracks and contact pads on ICs
Uses:
Gold Electrodeposition
Au(I) COMPLEX [Au(CN)
2
]
-
[Au(SO
3
)
2
]
3-
[Au(CS(NH
2
)
2
]
2+
K 10
39
10
10
10
25
pH 311 59 <1
[Au+] / g l
-1
450 320 10 20
T / C 3060 4060 25 50
ddc / A dm
-2
0.11.5 0.25 0.5 0.1 1.5
Acidic Thiourea Electrolyte
Formamidine Disulphide (FDS)
2(H
2
N)
2
CS (HN)
2
(H
2
N)
2
C
2
S
2
+2H
+
+2e
-
E
0
= 0.42 V
Strong Adsorption: TU-Au, G
0
ad
~ -43 kJ mol
-1
Chemical and/or Anodic Oxidation
Thiourea (TU)
Formation of higher oxidation products possible
Au(I) - CS(NH
2
)
2
Electrolyte
Au[CS(NH
2
)
2
]
2
+
+ e > Au + 2 CS(NH
2
)
2
E
0
=0.35 V
TU 10
-1
; Au
+
10
-2
Au(I) - CS(NH
2
)
2
- H
2
SO
4
Electrochemical Behaviour
Characterisation of ECD gold films
PURE GOLD PLATING PROCESS DEVELOPMENT
Electro-synthesis and Characterisation
of Binary and Ternary Gold Alloys
Au-Ag ; Au-Sn
Ag-Au-Sn ; Ag-Au-Pd
[Au(TU)
2
+
] Reduction Potential
Au[CS(NH
2
)
2
]
2
+
+ e

Au + 2 CS(NH
2
)
2
H
2
SO
4
1 M, Au(I) 5 mM, 25 C / Au 99.9%
Stability Conditions: pH < 1 [Tu] / [Au
+
] > 5 25 < T < 50 C
Formal Potential
E
0
= 130 mV
vs Ag/AgCl (KCl 3M)
0.01 0.1 1
-50
0
50
100
150
200
E

v
s

A
g
/
A
g
C
l

/

m
V
log[TU / mol l
-1
]
Cyclic Polarisation
0.01 0.1 1 10 100
-800
-600
-400
-200
0
200
E

v
s

A
g
/
A
g
C
l

/

m
V
i / mA cm
-2
Au 99.9%- H
2
SO
4
1 M, Au
+
0.1 M, TU 1 M - 40C - 20 mV s
-1
Current Efficiency
CE and deposition potential for ECD Au on Si\Ta\Au(50nm)
from Au
+
0.1 M, TU 1 M, H
2
SO
4
1 M - 4 mA cm
2
and 40C
1E-3 0.01 0.1 1 10 100
-600
-400
-200
0
200
400
600


[TU] / M
No
0.01
0.1
1
E

v
s

A
g
/
A
g
C
l

/

m
V
i / mA cm
-2
1E-3 0.01 0.1 1 10 100
-600
-400
-200
0
200
400
600
i / mA cm
-2
H
2
SO
4
1 M, FDS 10 mM - 5 mV s
-1
- 25C
RSSR + 2 H
+
+ 2 e
-
2 Tu
E= E + 0,0295log([FDS][H
+
]
2
/[TU]
2
)
E
0
190 mV vs Ag/AgCl (3 M)
FDS Electroreduction
Pt Au
Cathodic Passivation Related to FDS Electroreduction
Electrodeposition cd restricted to 2 mA cm
-2
Weak Influence of Stirring and Temperature
Search for & Selection of ADDITIVES
Halides
Chloride and Bromide: relatively weak effects
dependent on concentration
Best Iodide
Acidic Thiourea Solution
Au(I) - CS(NH
2
)
2
- KI
Au 99.9% - Au
+
0.1 M, H
2
SO
4
1 M, TU 1 M - 25C 20 mV s
-1
0.01 0.1 1 10 100
-600
-400
-200
0
200
KI
No
3 mM
E

v
s

A
g
/
A
g
C
l

/

m
V
i / mA cm
-2
0 2 4 6 8 10 12 14 16
40
50
60
70
80
90
100
KI / mM
No
0.6
3
6
30

/

%
i / mA cm
-2
H
2
SO
4
1 M, TU 1 M, Au
+
0.1M - Si\Au, 40C
Current Efficiency
0 2 4 6 8 10 12 14 16 18
0.0
0.2
0.4
0.6
0.8
1.0

30 mM KI 3 mM
(111)
(200)
(220)
(311)
M
h
k
l
cd / mA cm
-2
Crystal Structure
Crystal Structure
1 10 100
0.0
0.2
0.4
0.6
0.8

(111)
(100)
(110)
(311)
M
h
k
l
[KI] / mM
H
2
SO
4
1 M, TU 1 M, Au
+
0.1M - Si\Au, 5 mA cm
-2
- 40C
Surface Morphology
KI 0.6 mM 4 mA cm
-2
KI 3 mM 5 mA cm
-2
KI 6 mM 5 mA cm
-2
No KI 4 mA cm
-2
Au
+
0.1M, Tu 1 M
H
2
SO
4
1 M - 40C
900s - Si\Ta\Au
KI 30 mM 5 mA cm
-2
Mechanical Properties
160-190 110-180 70-100 60-90 HV -Hardness
20 g
Sulphite
Acid
Cyanide HG
Neutral
Cyanide
Alkaline
Cyanide
0 5 10 15
50
100
150
200
i / mA cm
-2
0 5 10 15
50
75
100
125
150
3 mA cm
-2
900s 40C KI 5g/l 900s 40C
100 1000
50
100
150
200
H
V

1
0
m
N
[KI] / ppm
50
75
100
125
150
100 1000
E

/

G
P
a
Conclusion
Gold Electrodeposition from simple acidic
thiourea solution is characterised by cathodic
passivation
Addition of halides (in particular iodide)
reduce interface inhibition and greatly extends
the range of deposition cd of practical interest
ECD Au from Au(I)-TU electrolytes is a viable
plating process
Thiourea based electrolytes are promising as
base solutions for Au alloys electrodeposition