Electro and Electroless Plating

- Fundamentals and Recent Trends

 Plating
Dry plating
CVD, Sputtering, Evaporation etc.
-- Thin film is obtained in vacuum or low pressure
environment (non-electrolyte)

Wet plating
Electroplating, Electroless plating
Immersion plating
-- Thin film is obtained from ion containing electrolyte
 General Applications

Metal electrowinning and electrorefining

Metal/alloy plating for decoration and
corrosion protection
Functional material electroplating
Electroless copper plating for PCB
 Brief Review

Electro and Electroless Plating

 Comparison of Metal Plating
Electroless Immersion
Property Eletroplating
plating plating
Driving Autocatalytic Chemical
External power
force redox reaction displacement
Cell reaction MAMC M2++RM+O M n++M1M+M1n+
Anode R, reducing M1 , dissolving
M or H2O
reactant agent in solution metal
M contaminated Pure metal
Nature of Pure metal (or
by O/R derived (porous and
deposit definite alloy)
species poorly adherent)
Thickness
1-100 1-100 <10
limit()
 Electroplating
current
_ _

e e

cathode O anode
H
2
2

H
_

+
OH
M +

M +

+ M
M
 Standard Electrode Potentials

K - Ca - Na - Mg - Al - Zn - Fe - (H) - Cu - Ag - Au

= =
Electrified Interfacial Region
- Double layer
 Electrified Interfacial Region
- Double layer
Double layer
Diffuse double layer
Compact double layer

Specifically adsorbed anion

+ Cu 2
+
Electrical
migration
Solution

+ Solvated cation +

- + Diffusion Diffuse double layer

Electrode + Activation energy Compact double layer

- + Cu substrate

+ Solvent molecule
IHP OHP

Input current => DC or Pulse

 Precipitation of Metal

Electric field is normal

to electrode surface
Charge transfer

kink

step
Surface diffusion
Electroless Plating
Catalyzed surface
substrate
R

e
M

M+
M+ + R catalyzed surface M + O
Immersion Plating

Substrate(M2)
M12+ M1
2e-
M22+ M2
 Electroless Plating

Deposition of a metal coating by a controlled

chemical reduction, catalyzed by the metal
or alloy being deposited
Deposition process is autocatalytic reaction
Electrons generated in-situ
Metal coatings on nonconductive substrate
Independent on geometry of substrate
Catalyzing Surface
(Activation)
 Chemical Reactions
NiP Electroless Plating

Ni2+ + H2PO2- + H2O Ni0 + H2PO3- + 2H+

H2PO2- + H2O H2PO3- + H2

Overall Reaction

Ni2+ + 2H2PO2- + 2H2O Ni0 + 2H2PO3- + 2H+ + H2

Secondary Reaction

H2PO2- + H H2O + OH- + P

 Chemical Reactions
Copper Electroless Plating

Cu2+ + EDTA4- Cu(EDTA)2- logK = 18.70

Ethylen-Deamin-Tetra-Acid C10H16N2O8

2HCHO + 4OH- 2HCOO - + 2H2O + H2 + 2e-

Cu2+ + 2e- Cuo

Overall Reaction

Cu (EDTA)2- + 2HCHO + 4OH -

Cuo + 2H2O + H2 + 2HCOO- + EDTA4-
Electro and Electroless plating

Advantages
Modest equipment demand and low cost process
Suitable to large scale plating
Fast kinetics

Disadvantages
Contamination or impurities in film
Reproducibility
Toxic waste generation
 Recent Applications
ULSI Application
Copper Metallization : IBM 1997
Replace aluminum Interconnects with copper

MEMS Application
LIGA (or LIGA- like process): 1990
Fabrication Microstructure by Electroforming
RF MEMS, Bio MEMS Fabrication

Packaging Application
UBM (Under Bump Metallurgy): 1997
Fabrication of Ni/Au by Electroless Plating
 Copper in Electronics

Low Resistance Copper Micro structure in RF MEMS Conducting layer in ULSI Copper metallization

Telecommunication R/F Board Solar cell

Copper On-Chip Interconnections
6 Level Copper Wiring Structure

C.Andricacos, Interface, Vol.8, No.1, 1999

 Aluminum vs. Copper
Electrical resistance comparison

C.Andricacos, Interface, Vol.8, No.1, 1999

 Comparison of Al and Cu

Al Cu
Resistivity () 2.8 1.7
Melting point () 660 1083
EM endurance (normalized to Al) 1 20
Heat of formation of oxide (/mol) -400 -40
Thermal exp. Coeff (1/K) 23.210-6 16.1210-6
Diffusion into SiO2 No Yes
Agglomeration No small
RIE easy difficult
Electromigration
 Damascene Process
Seed layer
(By Electroless plating,
MOCVD,Sputtering)
SiN
Barrier

Insulator deposition Barrier and seed layer deposition

Via
Plated metal
Insulator

Via definition Electroplating

Line
Via
Line definition CMP
Early stages of plating Late stages of plating

anti-conformal void

conformal seam

Super-filling defect-free
 Role of Additives

Inhibitor
Accelerator
CMP

Cu Cu
Super filling

K.W.Lee et.al, J.Korea ECS Vol.2 , No.4 , 1999

 Copper Growth in Trench

300nm 250nm 200nm

T. P.Moffat, J. of ECS, 2000

Cu-filled Via

V. Dubin et.al , ECS Proc. Vol. 98-6

MEMS Application
 LIGA Process

Fabricated photoresist molds Electroforming Remove photoresist

LIGA is the abbreviation of Lithographie Galvanik Abformung (German)

 Gold Electroplating

Inverted overlay coplanar waveguide

Micro cantilever array for mechanical
(IOCPW) transmission line for
characterization
millimeter-wave RF MEMS application
Nickel Electroplating

3-D wedge structure

Double Electroplating (Ni & Au)

Free Standing Microstructure

C.W. Baek & Y. K. Kim, KECS MEMS Conf. 2000

 Manipulation of Cells with
Mechanical Contact

Microgripper (C. J. Kim et. al.)

Micropippet for Microsurgery
Localized Electroplating of Copper

Aspect ratio 80

Microantenna
E. M. El-Giar, J. of ECS, 2000
 Nanowire Electroplating

200nm dia, 50m tall 40nm dia, 5m tall

Bi2Te3 Nanowire
J. P. Fleurial, Interface 2002
Packaging Application
Flip Chip Technology
Electrochemical Process in UBM

Bump Au

Zincate
Layer
Ni

Si Al

Zincate: Immersion plating

Ni: Electroless plating
Au: Electroless plating
Bump: Electroplating*
Schematics of Zincate Process
Electroless Nickel Plating on Zn
Electroless Nickel Plating

PCB Microbumps

S. Zhang, J. of ECS, 1999

Solder Bump on UBM

Pb-Sn Microbumps
IC interconnect
Important Process Requirements
- Electro and Electroless plating

Adhesion
Uniformity
Reliability
Reproducibility
 Summary
1. The electro and electroless plating are re-emerging
coating technologies in electronics industry.

2. Plating techniques are the case sensitive technique.

And then precise control of operating conditions
are required.

3. The inter-disciplinary collaborations is essential for

successful outcomes.

4. Roles of metallurgists become more important for

the reliable thin film processing.