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

Property

Eletroplating

Electroless
plating

Immersion
plating

Driving
force

External power

Autocatalytic
redox reaction

Chemical
displacement

Cell reaction

MAMC

M2++RM+O

M n++M1M+M1n+

Anode
reactant

M or H2O

R, reducing
agent in solution

M1 , dissolving
metal

Nature of
deposit

Pure metal (or

definite alloy)

M contaminated
by O/R derived
species

Pure metal
(porous and
poorly adherent)

Thickness
limit()

1-100

1-100

<10

Electroplating
current
e

cathode

OH

M
M

anode

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

2

Cu

Solvated cation

Electrode

+
IHP

Solution

Electrical
migration

Diffusion

Diffuse double layer

Activation energy Compact double layer

Cu substrate

+
Solvent molecule

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
M

O
M+
M+ + R

catalyzed surface

M + O

Immersion Plating

M1

M22+

2eM2

Substrate(M2)

M12+

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

H2PO2- + H2O

Ni0 + H2PO3- + 2H+

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 + 4OH2HCOO - + 2H2O + H2 + 2eCu2+ + 2eCuo

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

Telecommunication R/F Board

Conducting layer in ULSI Copper metallization

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

Resistivity ()
Melting point ()
EM endurance (normalized to Al)
Heat of formation of oxide (/mol)
Thermal exp. Coeff (1/K)
Diffusion into SiO2
Agglomeration
RIE

Al
2.8
660
1
-400
23.210-6
No
No
easy

Cu
1.7
1083
20
-40
16.1210-6
Yes
small
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

(IOCPW) transmission line for
millimeter-wave RF MEMS application

Micro cantilever array for mechanical

characterization

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

Ni

Au
Zincate
Layer

Si

Zincate: Immersion plating

Ni: Electroless plating
Au: Electroless plating
Bump: Electroplating*

Al

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.