Contamination and Cleanliness IMAPS 2010 06

Craig Hillman
Contamination and Cleanliness

Developing Practical Responses to a
Challenging Problem
IMAPS-Nordic Gotenborg, Sweden June 8, 2010
2004 - 2007
5110 Roanoke Place, Suite 101, College Park, Maryland 20740
Phone (301) 474-0607 Fax (240) 757-0053
www.DfRSolutions.com
2004 - 2009
2
Outline
Overview of Contamination
and Cleanliness
Motivation
Trends
Drivers
Temperature
Humidity / Moisture
Voltage and Electric Field
Contamination
Sources of Contamination
Printed Board Fabrication
Fluxes / Assembly
Handling
Use Environment
Detection and Measurement
Types of Equipment and
Processes
Industry Best Practices
Contamination Limits
Mitigations
Cleaning
Conformal Coating
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Motivation / Trends
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4
Why Contamination and Cleanliness?
Believed to be one of the
primary drivers of field
issues in electronics today
Induces corrosion and metal migration
(electrochemical migration ECM)
Intermittent behavior lends itself to
no-fault-found (NFF) returns
Driven by self-healing behavior
Difficult to diagnosis
Pervasive
Failure modes observed on batteries, LCDs, PCBAs, wiring,
switches, etc.
Will continue to get worse
2004 - 2007
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Future of Contamination / Cleanliness
Continued reductions in pitch between conductors will make
future packaging more susceptible
Increased use of leadless packages (QFN, land grid array, etc.)
results in reduction in standoff
Will reduce efficiency of cleaning, which may lead to increased
concentration of contaminants
Increased product sales into countries with polluted and tropical
environments (East Asia, South Asia, etc.)
ECM occurrence very sensitive to ambient humidity conditions
Pb-Free and smaller bond pads
Require more aggressive flux formulations
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The Future: Reduced Spacings
Critical distance effect?
Two studies by DfR staff
NaCl seeding
Conformal coating over no-clean flux residues
Over 300 coupons tested (IPC-B-25)
6.25, 12.5, and 25 mil spacings; 40C/93%RH, 65C/88%RH,
85C/85%RH
No ECM at 25 mil spacings
Experience based on
older designs may not
be valid
Test coupons must
have the same spacing and
same electric field as actual
product
2 mil (48 m) BGA Substrate Traces
4 mil (100 m)
PCB External Traces (low
voltage line)
7 mil (170 m)
Thin Shrink Small Outline
Package (TSSOP) Leads
5 mil (120 m)
Peripheral Flip Chip Solder
Bumps
Spacing Parameter
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QFN and Dendritic Growth
Large area, multi-I/O and low standoff can trap flux
under the QFN
Processes using no-clean flux should be requalified
Particular configuration could result in elevated weak
organic acid concentrations
Those processes not using no-clean flux will likely
experience dendritic growth without modification of
cleaning process
Changes in water temperature
Changes in saponifier
Changes to impingement jets
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QFN and Dendritic Growth (cont.)
The electric field strength between adjacent conductors is a
strong driver for dendritic growth
Voltage / distance
Digital technology typically has a maximum field strength of
0.5 V/mil
TSSOP80 with 3.3VDC power and 16 mil pitch
Previous generation analog / power technology had a maximum
field strength of 1.6 V/mil
SOT23 with 50VDC power and 50 mil pitch
Introduction of QFN has resulted in electric fields as high as
3.5 V/mil
24VDC and 16 mil pitch
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QFN and Dendritic Growth (cont.)
Some component manufacturers are aware of this
issue and separate power and ground
Linear Technologies (left) has strong separation power and
ground
Intersil (right) has power and ground on adjacent pins
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Higher Activity Flux
Reduced bond pads = smaller volumes of solder paste (less flux)
Oxide thickness remains the same
Requires higher activity fluxes
Copper
Copper
Oxide
Solder
Paste
6 mil stencils
4 mil stencils
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Drivers
Background on ECM
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Failure Mode
Why do you care about excessive
contamination or insufficient cleanliness lead
to?
Electrochemical Migration
(note: not Electromigration; completely different mechanism)
Understanding the mechanism provides
insight into the drivers and appropriate
mitigations
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Electrochemical Migration (ECM)
Defined, per IPC-TR-476A, Electrochemical
Migration: Electrically Induced Failures in
Printed Wiring Assemblies (1997), as
The growth of conductive metal filaments or
dendrites on or through a printed board under the
influence of a DC voltage bias
Too narrow
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What is ECM?
Alternative definition
Movement of metal through an electrolytic solution under
an applied electric field between insulated conductors
Electrochemical migration can occur on or in almost
all electronic packaging
Die surface
Epoxy encapsulant
Printed board
Passive components
Etc.
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ECM Mechanisms
Some ECM Mechanisms have more definitive
descriptions
Dendritic growth
Descriptor for ECM along a
surface that produces a
dendrite morphology
Tree-like, Feather-like
Conductive anodic filaments
(CAF)
Descriptor for migration within
a printed circuit board (PCB)
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ECM Steps
Traditional electrochemical migration involves
four steps
Path formation
Electrodissolution
Ion migration
Electrodeposition
In ECM along internal surfaces (e.g., CAF),
ion migration / electrodeposition co-exist
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Path Formation
Physio-chemical changes necessary to initiate ECM
Different meanings for different mechanisms
Believed to be the rate-limiting step
Dendritic growth
The creation of an electrolytic solution sufficiently
conductive
Driven by relative humidity, contaminants,
delamination
Conductive anodic filaments (CAF)
Degradation of the epoxy/glass interface
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Electrodissolution
Minimum requirements
Electric field and a polar liquid
Usually water
Voltage > Anodic
electromagnetic force (EMF)
0.34 volts for Cu
Electrochemical reaction
usually occurs adjacent to
anode
2H
2
0 O
2
+ 4H
+
+ 4e
-
Increased concentration of H
+
reduces pH to below 7.0
Dissolution of anode material (Cu)
Cu Cu
+
+ e
-
or Cu Cu
2+
+ 2e
Halides are not required to induce dissolution

Can increases susceptibility through changes in ion formation
Reduction in pH; increases solubility of metal ions (i.e, copper)
Cu
+2
H
+ H
2
H
+
H
+
Copper
e e
H
+
H
+
Cu
2
O
CuO Cu
2
O
NaCl
NaCl
Na
+
Cl
-
Cl
-
Na
+
CuCl
H
2
O +
Cu
2
O
Cl
-
CuCl
+
+
H
+
H
2
H
+
Cl
-
Cu
+2
Pure Water --
Cu
+1
Chloride --
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Ionic Migration
D
e
c
r
e
a
s
i
n
g

p
H
v = E = q/(6r)
v is velocity, is mobility, E is field strength, q is charge, r is ionic radius, is viscosity
Also known as electrophoresis
Migration of charged
particles through a solution
under the influence of an
electric field
Positive ions travel along the
field lines
From anode to cathode
Electrons travel in reverse
direction
Velocity can be computed
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Electrodeposition
Once ions reach the cathode, electrochemical reactions occur:
O
2
+ 2H
2
0 + 4e
-
4OH -
2H
2
0+ 2e
-
2OH
-
+ H
2
Cu
+
+ e
-
Cu or Cu
2+
+ 2e
-
Cu
Because cathodic electrodeposition is largely diffusion controlled, rate
depends on the metal ion concentration in the aqueous medium
Production of hydroxyl ions (OH-) at cathode can reduce the rate of
electrodeposition by combining metal ions with hydroxyl ions to form
hydroxides
Hydroxides remove metal ions from aqueous medium through partial
precipitation
Thus, ECM rate is correlated with the solubility product of the metal ion
hydroxide
Ionic contaminates, such as Cl -, can further change the ECM rate by
forming alternate reaction paths and by forming additional ionic species,
Example: CuCl in the case of copper and Cl
-
.
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Dendrite Propagation
Growth along preferential
crystallographic directions
Creates tree-like
appearance
Primarily along (111) plane
Branches in the [211] and
[110] directions
(111) is a close-packed (CP)
plane in FCC structures.
Most metals are FCC
CP planes are slip planes
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Drivers
Temperature / Moisture
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ECM Drivers: Electrolytic Solution
Comprised of water and ions (thin film of moisture)
Where does the water come from?
Ambient moisture in the air
Evaporation of absorbed moisture (surface ECM)
Measurement (techniques)
Adsorption -- Quartz crystal, Ellipsometry
Absorption -- Weight gain
Measurement (units)
Adsorption -- Monolayers of moisture, or areal mass density (ng/cm
2
)
1 monolayer = 31 ng/cm
2
Absorption -- Percent change in weight
How much water?
Very dependent upon relative humidity
Relatively insensitive to temperature
Even for moisture absorption (numerous internal interfaces)(faster diffusion)
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Water Adsorption (Metals)
Leygraf and Graedel, 2000
Lee and Staehle, 1997
Metals
2
4
6
8
10
M
o
n
o
l
a
y
e
r
s
o
f

M
o
i
s
t
u
r
e
0
Copper
Marcus, 2002
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Water Absorption
0.00
0.05
0.10
0.15
0.20
0.25
0 5 10 15 20 25 30 35
Time
1/2
(hour
1/2
)
M
o
i
s
t
u
r
e

C
o
n
t
e
n
t

(
%
)
85
o
C/85%RH
40
o
C/93%RH
Epoxy encapsulant
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Monolayers of Moisture
Insulator Material
_
Anode
Cathode
Most measurements performed on
non-porous solids (metals, ceramics)
Surface of interest for ECM tends
to be polymeric (solder mask, FR4,
encapsulant)
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Moisture Adsorption (Polymer)
Monolayers over polymer
difficult to measure
Dueling processes of
adsorption and absorption
Influenced by surface
properties (hydrophilic,
hydrophobic), bulk properties,
and porosity
Parameters rarely measured
by materials supplier
Actual number of monolayers
over polymeric surface as a
function of relative humidity is
debatable
Estimate of few to several
hundred
ECM possible > 80%RH
ECM likely Condensation
ECM unlikely 60 80%RH
ECM rare < 60%RH
General guidelines
Partially dependent upon ionic solubility
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Deliquescence
Dissolution of ionisable
residues
Resistance change can be
several orders of magnitude
(der Marderosian, 1977)
Each inorganic compound
has a different critical RH
HCl contaminated
substrates
Dilution of contaminants at
70%RH (Zamanzadeh,
1989)
%RH
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Condensation
What is condensation?
When surface moisture becomes visible?
The amount of adsorbed moisture at 100%RH?
Definition somewhat unclear
Film thickness can range (metals)
Minimum (10 monolayers of moisture)
Dew (~1,000 monolayers of moisture)
Raindrops (~10,000 monolayers of moisture)
When does condensation occur?
At 100%RH
When the surface temperature is below the dew point
temperature
Presence of cracks and delaminations
Hygroscopic
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Problems with Condensation
Mimics behavior of bulk water
Large decrease in resistance
5 monolayers has conductivity two orders of magnitude lower
than bulk water
20 monolayers has a conductivity one order of magnitude
lower
Dissolution of additional surface contaminants
Rapid decrease in time to failure
Days to seconds
Changes in migration behavior
Larger distances
Over alternative surfaces (e.g., conformal coating)
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*From Contamination Studies Laboratory, Inc., http://www.residues.com
Elapsed time 12 sec.
Dendritic Growth during Water Drop Test
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Pin to pin migration over conformal coating
Dendritic
Growth
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Cracks and Condensation
Vapor pressure of water in a crack is reduced
Condensation of liquid occurs when partial
pressure matches reduced vapor pressure
Water molecules adsorb to surface; first
layers bonding energy is comparable to
chemical bond
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Capillary Condensation
ln RH = -2v/RTd, where
is surface tension of water (~80 dyne/cm)
v is molar volume (18 cm
3
/mole)
R is gas constant (107 dynecmmole
-1
K
-1
)
T is absolute temperature
d is crack opening
d
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Cracks and ECM
Greatly reduces humidity
necessary to induce
condensation
Why ECM in cracked chip
capacitors happens
relatively rapidly
Why conformal coating
must adhere to the board
surface
Why popcorning results in
elevated leakage currents in
plastic encapsulated
microcircuits (PEMs)
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Hygroscopic Residues
Certain contaminants create conditions that
increase moisture film thickness
Increase risk of condensation
Ionic and non-ionic contaminants
Examples: Polyglycols
When present, turns surface from hydrophobic
(water repelling) to hydrophilic (water attracting)
Non-ionic: Not detectable using ion
chromatography or Omegameter
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Lessons to Learn
Do not underestimate relative humidity in controlled
environments (telecom, server, storage)
Macro environment controlled to 40-60%RH
Micro environments can easily exceed 80%RH or greater for
long periods of time
Case study
Failure of hard drive controller due to ECM internal to the epoxy
encapsulant
Environmental tests by DfR Solutions staff indicated ECM would
not initiate below a certain percentage of moisture absorption
Equivalent to 82%RH
Drivers
Minimal power dissipation during standby
Use of metal enclosure (minimal air flow)
Possible outgassing of absorbed moisture from polymeric materials
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Lessons to Learn (cont.)
Do not overestimate potential for condensation in
uncontrolled environments
Temperature rise of 5C often sufficient to prevent
condensation
Constant power on
Excessive condensation can initiate corrosion over
conformal coating
Critical focus
Cleanliness
Housing design (prevent physical water from coming into
contact with board surface)
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Drivers
Voltage / Electric Field
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Electric Field (Voltage/Distance)
Voltage is a primary driver in two processes
Electrodissolution (oxidation reaction)
Ion Migration
Electrodissolution
Applied voltage must exceed EMF
0.13 V for Sn/Pb, 0.25 V for Ni, 0.34 V for Cu,
0.8 V for Ag, and 1.5 V for Au
Ion migration
Force on the ions, and therefore velocity, is a function of
electric field strength
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Electric Field Strengths (Nominal)
Logic devices
Previous generation
6.4 V/mm (SO32 --
1.27 mm pitch, 5 VDC)
Current generation
20 V/mm (TSSOP80 --
0.4 mm pitch, 3.3 VDC)
Power devices
Previous generation
64 V/mm (SOT23 --
Current generation
140 V/mm (QFN
Copper traces: 240 V/mm (0.5 mm spacing, 120 VDC)
IPC-2221A allows 300 V/mm (0.1 mm spacing, 30 VDC)
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Copper traces
120 VDC with 20 to 30 mil spacing (5 to 6
V/mil)
IPC allows 15V / mil (IPC-2221A)
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Electric Field (cont.)
Prior studies have demonstrated varying effects of
electric field on ECM
DfR (seeding of IPC-B-25 coupons with NaCl)
6V / 6.25 mil = 1 V/mil (dendritic growth)
42V / 25 mil = 1.7 V/mil (no dendritic growth)
Undefined combination of electric field and spacing to
initiate ECM
Conductive anodic filament (CAF) growth models
have demonstrated conflicting behavior
V/d, V/d
2
, V/d
3
, and V/d
4
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E-Field and Contamination
0.0
1.0
1.5
2.0
0.5
6 10
14 18
Halide concentration (g/in
2
)
E
l
e
c
t
r
i
c

F
i
e
l
d

(
V
/
m
i
l
)
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E-Field and Dendritic Growth
Immersion silver (Ag)
plating
85C / 85%RH / 10VDC
Observation
Migration only at tip of
comb pattern
Dendrites stopped growing
Why?
Maximum electric field
strength
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Electric Field Strength (ImAg Migration)
E-field (6.25 mil spacing) E-field (12.5 mil spacing)
E
max
= 3.50 V/mil E
max
= 3.02 V/mil
At 85C/85RH, the critical electric field strength to initiate
silver migration is between 3.0 to 3.5 V/mil
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Drivers
Contamination
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Contamination
Two concerns
Hygroscopic contaminants (discussed)
Ionisable contaminants that are soluble in water (e.g., acids,
salts)
Ionic contaminants of greatest concern
Primarily anions; especially halides (chlorides and bromides)
Chemically aggressive due to chemical structure
Very common in electronics manufacturing process
Decreases pH; few metal ions found in dendrites are soluble at mid
to high pH. Cu dendrites require pH less than 5 to form.
Silver(I) ions are soluble at higher pH; reason it is one of easiest to
form dendrites.
Cations primarily assist in the identifying the source of anions
Example: Cl with K suggests KCl (salt from human sweat)
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Sources of Contaminants
Printed board fabrication process
Insufficiently cured polymers
Rinse water
Fluxes
Handling
Storage and use environment
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Sources of Contaminants (cont.)
Rinse Water NO
4
Solder Flux Weak Organic Acids
Rinse Water, Air Pollution, Papers/ Plastics SO
4
Cleaners, Red Phosphorus PO
4
Teflon, Kapton Fl
Printed Board (flame retardants), HASL Flux Br
Board Fab, Solder Flux, Rinse Water, Handling Cl
Possible Sources Ion
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Printed Board Fabrication Process
One of the most common source of
contaminants
Greatest use of active/aggressive chemicals
Low margin business (reverse auctions)
Increasing use of no-clean assembly process (last
chance to clean)
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PCB Contaminants (examples)
Etching
Chloride-based: Alkaline ammonia (ammonium chloride), cupric chloride,
ferric chloride, persulfates (sometimes formulated with mercuric chloride)
Other: Peroxide-sulfuric acid
Neutralizer
Hydrochloric acid
Cleaning and degreasing
Hydrochloric acid, chlorinated solvents (rare)
Photoresist stripping
methylene chloride as a solvent
Oxide
Sodium chlorite
Electroless plating
Sodium hypochlorite (in potassium permanganate)
Palladium chlorides (catalyst)
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Printed Board Fab (other examples)
Bromide sources
Surface processes
Solder masks, marking inks, and fluxes
Flame retardant
FR-4 Epoxy has used a brominated bisphenol A (TBBA)
epoxy resin
IPC-TR-476A: Bromide in epoxy resin can diffuse to the
surface during a high temperature process such as
soldering
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Source of Contaminants: Fluxes
Chemicals used for preparing metal surfaces for soldering
High molecular weight chemistries
Slightly acidic
Optimum behavior
Maximum activity during reflow; minimum activity after reflow
Difficult balancing act
Flux nomenclature
Rosin only (RO)
Rosin, midly activated (RMA)
Rosin activated
Water soluble
Low residue (no-clean)
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Flux Chemistry
Two types: Rosin and Water-Soluble (WS)
No-clean can be rosin (Indium 3549-HF) or water-soluble
(Kester 977)
No-clean based on ability to pass surface-insulation
resistance (SIR) and electrochemical migration (ECM) tests
Initial classifications from military (Mil-F-14256E);
primarily focused on rosin-based fluxes
Rosin/Resin (R), Rosin Mildly Activated (RMA), Rosin
Activated (RA), Rosin Super Activated (RSA)
Primarily R and RMA used for electronics assembly; some
RA
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J-STD-004 Flux Classification
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J-STD-004 (cont.)
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Materials (Definition)
Rosin: Derived from tree sap. Mix of abietic acid and other
compounds
Resin: Natural and synthetic compounds designed to act like
rosin
Organic (aka OA): Solution of organic acids and other
compounds (hydrohalides, amines, and amides). Tend to be
water soluble since they contain no rosin
Inorganic: Solution of inorganic acids. Tend to be water
soluble since they contain no rosin. Not as common as
organic (very aggressive)
Activity levels based on Copper Mirror Test (IPC TM-650)
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Flux Classification Correlation
L0 - All R, Some RMA, Some Low Solids "No-Clean"
L1 - Most RMA, Some RA
M0 - Some RA, Some Low Solids "No-Clean"
M1 - Most RA, Some RSA
H0 - Some Water Soluble
H1 - Some RSA, Most Water Soluble
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Fluxes (cont.)
5% of the market uses rosin
Preferred in the early days of electronics manufacturing
Insoluble residues encapsulated contaminants
Hydrophobic surface
Quasi-conformal coating
This is decreasing (concerns regarding environmental-
friendliness of solvents required to clean)
25% uses water soluble fluxes
70% of the market uses no-clean
80-90% in consumer, computer, telecom markets
This is increasing
Fine pitch, low clearance, high density greatly decreases
cleaning effectiveness
Electronics industry very cost sensitive (eliminate one process,
increase throughput)
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No-Clean Flux Chemistry
Activators (weak organic acids) -- 0.5 - 5%
Wetting agents (surfactants) -- 1%
Polyglycols (polyethylene glycol & polypropylene glycol),
alkylenic ethoxylate, and fluorinated esters
Chealtors -- 1%
Reacts with green copper salts, formed from activators and
copper, to create clear or white copper products.
Masking so operator will not think of this as a corrosion product
Solvents -- remainder (93 98%)
VOC-free is primarily water; others are IPA, methanol, etc.
2004 - 2007
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2004 - 2009
62
Flux Residues
Residues of no-clean soldering?
Water-soluble dicarboxylic acids
Hygroscopic polyethylene glycol ethers
List of potential weak organic acids (WOAs)
Benzoic, Butyric, Formic, Lactic, Malonic, Oxalic, Propionic,
Succinic, Citric, Glutaric, Adipic, Malic
Optimum flux
Acids are neutralized after soldering process
Residual wetting agents are minimized
2004 - 2007
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2004 - 2009
63
Other Concerns
Combinatorial effects are not well known
Anecdotal indications of unexpected deleterious
reactions between fluxes (poor understanding of
the root-cause)
Reactions between fluxes and industrial pollutants
may also accelerate corrosive behavior
Excessive flux
Typically occur with wave, selective solder, and
hand soldering operations
2004 - 2007
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2004 - 2009
64
Handling / Storage / Environment
Handling
Salts from human contact (KCl and NaCl)
Storage
Cleaning chemicals
Outgassing
Polymeric materials
Use Environment
Dust
Evaporated sea water
Industrial pollutants
2004 - 2007
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2004 - 2009
65
Handling / Sweat
Composition of dissolved salts in water
Can include other biological molecules.
Main constituents, after the solvent (water),
Chloride, sodium, potassium, calcium, magnesium, lactate,
and urea.
Chloride and sodium dominate.
To a lesser but highly variable extent, iron, copper,
urocanate (and the parent molecule histidine), and other
metals, proteins, and enzymes are also present.
The main concern regarding sweat is as a source of
chloride
2004 - 2007
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2004 - 2009
66
Handling / Sweat (cont.)

0
20
40
60
80
100
120
140
160
Raw stock After Cleaning Handling (office) Handling
(exercise)
Handling (brow)
Type of Exposure
C
o
n
t
a
m
i
n
a
t
i
o
n

E
x
t
r
a
c
t
e
d

(
g
)
Chloride
Sodium
Potassium
Calcium
Magnesium
Lactic acid
0.14 1.20 0.36 0.00 0.39 46.61 0.00 Handling (after wiping brow) 5
0.09 0.92 0.41 0.00 0.39 25.63 0.00 Handling (after exercise) 4
0.10 1.30 0.41 0.00 0.49 14.35 0.00 Handling (office environment) 3
0.09 1.07 0.21 0.00 0.45 0.47 0.00 After polish and clean 2
0.07 1.00 0.26 0.00 0.43 2.14 0.00 Raw stock aluminum 1
SO
4
(g/in
2
)
PO
4
(g/in
2
)
NO
3
(g/in
2
)
Br
(g/in
2
)
NO
2
(g/in
2
)
Cl
(g/in
2
)
F
(g/in
2
)
ID
0.14 1.20 0.36 0.00 0.39 46.61 0.00 Handling (after wiping brow) 5
0.09 0.92 0.41 0.00 0.39 25.63 0.00 Handling (after exercise) 4
0.10 1.30 0.41 0.00 0.49 14.35 0.00 Handling (office environment) 3
0.09 1.07 0.21 0.00 0.45 0.47 0.00 After polish and clean 2
0.07 1.00 0.26 0.00 0.43 2.14 0.00 Raw stock aluminum 1
SO
4
(g/in
2
)
PO
4
(g/in
2
)
NO
3
(g/in
2
)
Br
(g/in
2
)
NO
2
(g/in
2
)
Cl
(g/in
2
)
F
(g/in
2
)
ID
2004 - 2007
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2004 - 2009
67
Influence of Pollutants: Creepage Corrosion
Recent field issues with printed circuit
boards (PCBs) plated with immersion
silver
Sulfur-based creepage corrosion
Failures in customer locations with
elevated levels of sulfur-based gases
Rubber manufacturing
Sewage/waste-water treatment plants
Vehicle exhaust fumes (exit / entrance
ramps)
Petroleum refineries
Coal-generation power plants
Paper mills
Landfills
Large-scale farms
Automotive modeling studios
Swamps
P. Mazurkiewicz , ISTFA 2006
2004 - 2007
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2004 - 2009
68 68
Creepage Corrosion Failure of ImAg
Corrosion product is semi-conductive (resistance of about 1Mohm).
Resistance decreases as humidity increases.
Traces sensitive to leakage current trigger the system failure.
Visual inspection required to identify failures (most are CNDs).
Initiation of
a short
2004 - 2007
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69 69
Creepage Corrosion Mechanism
Exposed Cu was consumed to form copper
sulfide that could cause electrical shorts.
2004 - 2007
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70
Creepage Corrosion: Observations
Galvanic corrosion
Failures at locations with thin or
absent immersion silver
Edge of solder mask, deep in plated
through hole barrel
Copper and silver in contact
Similar mechanism observed
with electroless nickel /
immersion gold (ENIG) plating
Corrosion of copper trace
at solder mask edge

Solder Mask
Laminate
Copper
Nickel
2004 - 2007
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71
Creepage Corrosion: Observations
Failure behavior not observed during
qualification testing [Mixed Flowing Gas
(MFG) Testing Class III]
Reason 1: Lack of appropriate structures in
test vehicle
Reason 2: Test conditions may not be
appropriate
Strong indication that creepage
mechanism requires that
one or more MFG test
parameters are exceeded
Especially %RH
Hillman: >75%RH
Cullen: 93%RH
---- 20050 305 20020 402 752 IV
20050 20050 205 10020 301 702 IIIA
---- 20050 205 10020 302 752 III
10020 20050 103 105 301 702 IIA
---- 20050 103 105 302 702 II
---- ---- ---- ---- ---- ---- I
SO
2
(ppb)
NO
2
(ppb)
Cl
2
(ppb)
H
2
S
(ppb)
Temp
(C)
RH
(%)
Class
2004 - 2007
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72
MFG Test Conditions
Are existing MFG test conditions still
relevant?
Different material system (silver, not copper)
Changing environment (is there more / less
pollution?)
2004 - 2007
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73
Industrial Pollutants (Sulfur-Based)
SO2
MFG Test
100ppb, 200ppb
Average annual outdoor
2-20ppb (USA)
25-100ppb (Asia)
24 hour
~150ppb (NAAQS / Telcordia)
150-600ppb (Industrial-USA)
100-1500ppb (Asia)
May not be critical for
sulfidation of silver
Rate independent of SO2
concentration
H2S
MFG Test
10ppb, 100ppb, 200ppb
Average annual outdoor/indoor
0.05 to 0.8ppb
24 hour (outdoors)
8 to 100ppb (State Regs)
24 hour (indoors)
500 to 20,000 ppb
May be more critical
70000
28500
10000
4075
500
200
10
4
10
4
1.5
0.6
H2S
40000
15300
10000
3800
1000
380
100
38
100
38
100 ug/m
3
38 ppb
SO2
Inside
industrial
Adjacent to
industrial
Urban with
heavy traffic
or industrial
Rural
Controlled
environment
Clean
room
IEC 60721-3-3
2004 - 2007
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74
Test Conditions (cont.)
Carbonyl Sulfide (COS)
Ignored by MFG
Outdoor levels can be higher than H2S
Nominal: 0.5 0.8ppb
Elevated: 80 ppb
Can be as corrosive
as H2S
2004 - 2007
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75
Test Conditions (Relative Humidity)
Influence of %RH somewhat
contradictory
Vernon reported a critical %RH
(70-80%)
Graedel reported an increasing
corrosion rate with increasing %RH
Driven by monolayers (ml) of
moisture
ln (ml) = 2.73 p/p0 - 0.366
(p/p0 is %RH)
Rice reported no influence of %RH
2004 - 2007
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76
Relative Humidity
Validation of Rices observation
%RH levels in ceramic hybrid and thick film resistors coated with
hydrophobic silicone likely low
Important differentiation by mechanism
Most references investigate the tarnish aspect of sulfidation
Creepage behavior is likely very sensitive to %RH
The rough surface of a polymeric material becomes
conducive to material transport once micro-condensation
within occurs.
Filling-in of surface pores may greatly reduce the adhesion of
the polymer surface
Allows forces created by volumetric expansion of corrosion
product to push the growth out to an adjacent conductor
2004 - 2007
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77
Discussion
Modification of MFG test specs may be appropriate
Elimination of SO2 gases
Increase in H2S concentrations (>200 ppb)
Possible intro of COS
Elimination or reduction of Cl2
Speculation that formation of
AgCl inhibits sulfidation of silver
Elevated Cl2 displays parabolic
behavior
Elevated H2S displays unlimited
growth
2004 - 2007
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78
Pollutants: Not Always in Industrial Settings
Chinese Drywall Cited in Building Woes
The drywall is emitting sulfur-based gases that are corroding
air-conditioner coils, computer wiring and metal picture frames.
Drywall blamed for A.C. failures
Air-conditioning coils have turned black, along with wiring,
piping and even silver jewelry.
"We have definitely identified that a combination of sulfide
gases are the cause of the corrosion," said Robert P. DeMott,
managing principal of Environ.
"Foul odors reported by people living in the homes may also be
caused by the combination of sulfur gases being released from
the drywall,
Chinese drywall class action lawsuit
LEE COUNTY, Fla. - The Lawsuit was filed against Knauf
Plasterboard Tianjin Co., LTD, The Knauf Group, Rothchilt
International Limited and the Banner Supply Company.
Known as "Chinese Drywall", it was manufactured oversees
and was made from waste materials. As a result, it emits
sulfur compounds that corrode copper wiring and other metals
found in homes.
Copper Corroded by Sulfur flumes
Drywall Sulfur Fumes Blamed for A.C. & Electrical Equipment failures
2004 - 2007
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79
Drivers
Others
2004 - 2007
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80
Insulation
The influence of insulation (migration surface) on
ECM is poorly quantified
Hydrophobic surfaces superior
Silicone
Solder mask / FR4 epoxy selection rarely based on
ability to resist ECM
Exposed epoxy glass is much more hydrophilic than most
solder mask materials
Greater concern and investigation with CAF
Degradation of insulation (epoxy/glass interface) results in
path formation
2004 - 2007
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81
Conductor Material
Conductors of concern
SnPb (solder)
Sn alloy (Pb-free solder, lead plating)
Copper (traces, connectors, component leads)
Silver (conductive adhesives, thick film resistor)
Nickel (capacitor electrodes, lead plating)
Gold (connector plating)
Harsanyi and Inzelt established a ranking of pure metals according to propensity
to migrate
Ag > Pb > Cu > Sn
Ag will migrate under temperature/humidity/bias unless special prevention
Alloying with an anodically stable metal such as palladium or platinum (MLCC)
Using an organic coating (immersion silver plating)
Using a metallic coating (SMT resistors)
Cu and SnPb will alternately migrate
Propensity for Pb-free solder to migrate more or less than SnPb has not been
definitively established
Disagreement over which is more migratable (Sn or Pb)
Gold requires contamination to migrate (typically chloride)
2004 - 2007
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82
Immersion Silver (ImAg)
Effect of NaCl contamination level
Minimal effect at levels below 10 g/in
2
Repressed dendritic growth at levels above 10 g/in
2
AgCl is less soluble in water than Ag
0 g/in
2
2 g/in
2
10 g/in
2
2004 - 2007
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83
Drivers
Time to Failure Models
2004 - 2007
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84
Drivers of ECM
Failure models can provide a more
quantitative understanding of the
primary drivers
2004 - 2007
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85
Time to Failure (TtF) Models for ECM
Relevant TtF models must include the
primary drivers of ECM
Electric field (voltage, distance)
Temperature
Relative humidity
Contamination
Other effects to consider
Conductor material
Insulator material
2004 - 2007
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86
Potential TtF Models
Fundamental chemical behavior
Arrhenius
Eyring
Experimental observations
Barton-Bockris
DiGiacomo
Similar corrosion-based mechanisms
Peck
Howard
CAF
2004 - 2007
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87
Arrhenius
Widely used to describe variety of chemical
reactions
Limited to temperature effects
=
kT
H
A t
f
exp
A = scaling constant
H = activation energy (eV)
k = Boltzmann constant (8.62 x10
-5
eV/K)
T = temperature (K)
2004 - 2007
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88
Arrhenius (Hornung)
Based on dendritic growth of silver through borosilicate glass under an
electric field
Activation energy determined to be 1.15 eV
Growth rate linear dependence on electric field.
No humidity effect
Not true ECM model (dry silver migration)
Proportionality constant must be empirically determined
= proportionality constant
G = electrode spacing
V = voltage
H = activation energy (eV)
k = Boltzmann constant
T = temperature (K)
=
kT
H
V
G
t
f
exp
2004 - 2007
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89
Eyring
Extension of Arrhenius equation
Takes into account multiple stresses and synergy with
temperature
Recommended by IPC SIR Handbook to determine acceleration
factors for ECM
Too comprehensive?
Number of stresses undefined
Number of unknowns increases twice as fast as the number of
stresses
Stress functions undefined (natural log, exponential, linear)
+ +
+ +
=
2 1
exp S
T
E
D S
T
C
B
kT
H
AT t
f
2004 - 2007
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90
Barton and Bockris
Based on dendritic growth of silver in an electrolytic cell
h = conductor spacing
= interfacial energy (metal/solution)
R = universal gas constant
T = temperature
F = Faraday constant
D = diffusion coefficient
c
= metal ion concentration

= overpotential (function of dendrite rad.)
i = current density at the dendrite tip
2 2
8
=
Dc F
RT h
t
f
as i
2004 - 2007
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91
Barton and Bockris
Contains a term for migrating metal ion concentration, but not for contaminant
concentration
Dual effect of temperature
Linear dependence
D = D0exp
No humidity term
Good general model for dendritic growth
Requires dendritic growth to be rate limiting step
No terms for path formation, electrodissolution, and ion transport
Influence of ionic contamination on the various parameters, such as the
interfacial energy, would have to determined theoretically or measured through
experimentation.
Zamanzadeh [11] reviewed this model
Concluded that [This] model does not give accurate growth predictions, but gives a
general indication of the functional dependence of growth on a variety of
electrochemical parameters.
2004 - 2007
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92
DiGiacomo
( )

v
H r kT
erfc e
kT
V V
zFD
r
MC
t
kT
H
T
f

2
ln
ln
2
1 1
2
0

C =ionic concentration (Ag
+
)
zF =electric field,
D
0
=diffusivity,
r =radius of curvature of the dendrite tip,
l/M =the critical amount of metal ions that must migrate to achieve dendritic growth,
=degree of oxidation or fractional active surface, changes from metal to metal,
V
T
=determined by the critical current density for dendritic growth,
H =activation energy, k =Boltzmann's constant, T =absolute temperature,
=ln(r
50
/r
16
), sigma for a lognormal distribution
Based on migration of silver in encapsulated packages
Derived from use of the Butler-Volmer equation
Relates electrode potential to current density
2004 - 2007
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93
DiGiacomo
Scientific curiosity unless current density can
be related to measurable physical factors
Current density is a function of conductance and
electric field
Conductance is function of contamination and
relative humidity.
Could be the basis of describing time to
failure in terms of contamination, relative
humidity, and e-field.
2004 - 2007
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94
Peck
t
life
= time to failure,A
0
= material constant
RH = relative humidity, n = empirical constant (2.66)
E
a
= activation energy, k = Boltzmann constant
T = temperature, f(v) = voltage function (power law, ~1.5)
( ) kT E v f RH A t
a
n
life
=

exp ) (
0
Galvanic corrosion of aluminum bond pads in encapsulated
microcircuits
Based on Eyring model
Review of previous research
Primary environments: 85/85, 110/85
Voltages: 5 to 70 VDC
2004 - 2007
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95
Howard
Based on corrosion of conductors on ceramic substrates
Derived from Faradays Law
Maybe applicable to Huawei situation
t MV
wlhndF
t
f
=
w = conductor width
l = conductor length
h = conductor thickness
d = density of conductor material
F = Faraday constant
M = atomic weight of conductor
V = voltage bias
= resistivity of electrolyte
t = electrolyte thickness
2004 - 2007
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96
Conductive Anodic Filament (CAF) Models
( )
( )
t
t
m
n
eff
f
M M
M M V
L f a
t >
= ,
1000
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97
ECM Time to Failure Behavior
Little interest in time to failure model for
dendritic growth
Why?
Under high humidity (>90%RH) testing, strong
experimental indications that rate limiting step
may be nucleation/initiation
Most data suggests ECM will initiate within 72 to
120 hours under test conditions, or not at all
Additional indicators
2004 - 2007
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98
Growth vs. Nucleation (1a)
Higher levels of stress result in failure mechanism shift
Prevents acceleration of mechanism
6.25 mils 6.25 mils
10 g/in
2
Br + 2 g/in
2
Cl 10 g/in
2
Br + 50 g/in
2
Cl
40C/93%RH / 10VDC / HASL Finish
G
r
o
u
n
d
/
A
n
o
d
e
P
o
w
e
r
/
C
a
t
h
o
d
e
2004 - 2007
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99
Growth vs. Nucleation (1b)
40C/93%RH 85C/85%RH
No-Clean Rosin-Based Flux / Urethane Conformal Coating
10VDC / HASL Finish
2004 - 2007
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100
Growth vs. Nucleation (2a)
Many drivers have critical stress levels
Relative humidity for deliquescence
Voltage for electrodissolution
Contaminant levels for ECM
Time to Failure
Stress
Wide variation in time
to failure over range of
stresses not observed
for ECM
2004 - 2007
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101
Growth vs. Nucleation (2b)
Direct evidence of critical
electric field strength
Recent study performed on
a dummy microcircuits of
copper on silicon
Dendrite formation instantaneous at right conditions
(presence of oxalic acid)
0.4V at 3m spacing
1.2V at 10m spacing
2004 - 2007
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102
Growth vs. Nucleation (3)
Dendritic morphology suggests dependence on
nucleation
6.25 mils
6.25 mils
Heterogenous nucleation Homogenous nucleation
2004 - 2007
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103
Growth vs. Nucleation (4)
Where else are dendrites observed?
Solidification of liquid metal
Analogy
Copper ions in solution nucleate on the walls of
the cathode conductor (heterogeneous)
Solidification consist of nucleation and growth
At supercooled conditions, nucleation behavior
dominates
2004 - 2007
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104
Preventing ECM
If nucleation-dependent, shift should be away
from predicting time to failure and towards
preventing failure
The most effective method is through tight
controls of contamination
2004 - 2007
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105
Contamination / Cleanliness
Detection, Measurement, and Requirements
2004 - 2007
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106
How to Measure Cleanliness?
Standard ion chromatography (IC) testing
IPC-TM-650, Method 2.3.28A
Submerge whole board; 75 IPA / 25 DI
Updated IC
IPC-TM-650, Method 2.3.28.2
Submerge whole board; 10 IPA / 90 DI (Delphi requirements)
Modified IC
Use of saponifiers or alternative solvent
Submerge whole board
Localized Testing
C3 from Aqueous Technologies
2004 - 2007
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107
PCB Cleanliness Control: Industry Specs
IPC-6012B, Qualification and Performance
Specification for Rigid Printed Boards, Section 3.9
Requires confirmation of board cleanliness before solder
resist application
When specified, requires confirmation of board cleanliness
after solder resist or solderability plating
Board cleanliness before solder resist shall not be
greater than 10 ug/in
2
of NaCl equivalent (total
ionics)
Based on military specifications from >30 years ago
Board cleanliness after solder resist shall meet the
requirements specified by the customer
2004 - 2007
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108
Cleanliness Control: Test Procedures
IPC-6012B specifies a Resistance of Solvent Extract
(ROSE) method
Defined by IPC-TM-650 2.3.25
IPC-6012B specifies this measurement should be
performed on production boards every lot
Class 1 boards: Sampling Plan 6.5
Class 2 and 3 boards: Sample Plan 4.0
Sampling plan (example)
If a lot contains 500 panels of a Class 2 product, 11 panels
should be subjected to ROSE measurements for
cleanliness testing
2004 - 2007
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109
Test Procedures: Common Problems
ROSE is the least sensitive of ionic measurement techniques
5 ug/in
2
detected by ROSE is equivalent to ~20 ug/in
2
detected by ion
chromatography
Equipment is not calibrated
Insufficient volume of solution is used
Insufficient surface area
Panels are preferred over single boards
Cut-outs are not considered when calculating surface area
Insufficient measurement time
7 to 10 minutes is preferred
Technique Technology Equivalency Factor
ROSE Static / Unheated 1
Omega-Meter Static / Heated ~1.5
Ionograph Dynamic / Heated ~2.0
Modified-ROSE, Zero-Ion, etc. Varied ~4.0 (?)
Ion Chromatography 80C for 1 hr ~4.0
2004 - 2007
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110
Test Procedures: Best Practice
Ion Chromatography (IC) is the gold standard
Some, but very few, PCB manufacturers qualify lots
based on IC results
Larger group uses IC to baseline ROSE /
Omegameter / Ionograph (R/O/I) results
Perform lot qualification with R/O/I
Periodically recalibrate with IC (every week, month, or
quarter)
2004 - 2007
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111
Cleanliness Control: Requirements
The majority of knowledgeable OEMs
completely ignore IPC cleanliness requirements
Option 1: Requirements are based on
R/O/I test results, but adjusted for lack of
sensitivity
Most companies now specify 2.5 to 7 ug/in
2
Option 2: Requirements are based on IC test
results and then monitored using R/O/I
2004 - 2007
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112
PCB Cleanliness: Moving Forward
Extensive effort to update PCB Cleanliness Standards
IPC-5701: Users Guide for Cleanliness of Unpopulated
Printed Boards (2003)
IPC-5702: Guidelines for OEMs in Determining Acceptable
Levels of Cleanliness of Unpopulated Printed Boards (2007)
IPC-5703: Guidelines for Printed Board Fabricators in
Determining Acceptable Levels of Cleanliness of Unpopulated
Printed Boards (Draft)
IPC-5704: Cleanliness Requirements for Unpopulated
Printed Boards (2010)
2004 - 2007
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113
PCB Cleanliness (cont.)
The old 10 ug/in
2
(1.56 ug/cm
2
) being replaced
Driven by Delphi requirements
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Nominal Ionic Levels
Bare printed circuit boards (PCBs)
Chloride: 0.2 to 1 g/inch
2
(average of 0.5 to 1)
Bromide: 1.0 to 5 g/inch
2
(average of 3 to 4)
Assembled board (PCBA)
Chloride: 0.2 to 1 g/inch
2
(average of 0.5 to 1)
Bromide: 2.5 to 7 g/inch
2
(average of 5 to 7)
Weak organic acids: 50 to 150 g/inch
2
(average of 120)
Higher levels
Corrosion/ECM issues at levels above 2 (typically 5 to 10)
Corrosion/ECM issues at levels above 10 (typically 15 to 25)
Corrosion/ECM issues at levels above 200 (typically 400)
General rule
Dependent upon board materials and complexity
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115
Cleanliness Controls: Ion Chromatography
Contamination tends to be controlled through industrial
specifications (IPC-6012, J-STD-001)
Primarily based on original military specification
10 g/in
2
of NaCl equivalent
Calculated to result in 2 megaohm surface insulation resistance (SIR)
Not necessarily best practice
Best practice is contamination controlled through ion
chromatography (IC) testing
IPC-TM-650, Method 2.3.28A
*Based on R/O/I testing
Pauls
General
Electric
NDCEE DoD* IPC* ACI
Chloride (g/in
2
) 2 3.5 4.5 6.1 6.1 10
Bromide (g/in
2
) 20 10 15 7.8 7.8 15
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116
Major Appliance Manufacturer (IC)
Incoming PCB Processed PCB
Contaminant
Maximum Level
(ug/in
2
)
Maximum Level
(ug/in
2
)
Upper Control Limit
(ug/in
2
)
Ammonium <0.5 <2
Bromide 3 10 8
Calcium <0.5 <1
Chloride 2.5 3.5 3
Fluoride <0.5 <1
Magnesium <0.5 <1
Nitrate <0.5 <2
Nitrite <0.5 <1
Phosphate <0.5 <1
Potassium <3 <3
Sodium <3 <3
Sulfate 3 3 2
Total 5 18 14
Weak Organic Compounds 200 200 50

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DfR Solutions IC Requirements
200 150 Total Weak Organic Acids
6 4 Sulfate
6 4 Phosphate
6 4 Nitrite
6 4 Nitrate
2 1 Fluoride
4 2 Chloride
15 10 Bromide
Maximum Level
(g/in
2
)
Upper Control Limit**
(g/in
2
)
Contaminant
**Upper control limits may be considered maximum levels
for high reliability applications or products used in
uncontrolled environments
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Mitigation -- Cleaning
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PCB Cleaning: Process Flow
At a minimum, PCB manufacturers should clean the
PCB:
Immediately before the application of solder resist
Immediately after the application of any solderability plating
HASL
Electroless Nickel and Immersion Gold
Immersion Tin
Immersion Silver
Some PCB manufacturers also perform a final clean
Should not substitute cleaning after solderability plating
Residues from plating operations can become more difficult
to remove with any time delay
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120
PCB Cleaning Process: Requirements
Final rinse with deionized (DI) water
2-8 M is preferred; >10 M may be too aggressive
Distilled water is insufficient
City water is unacceptable
Potential options
Use of saponifier during the cleaning process
Heated DI water is nice, but not absolutely necessary
Common problems
DI water is only used if specified by the customer
DI water is turned off to reduce water and energy usage
Failure to monitor DI water at the source
Failure to alarm the DI water on the manufacturing floor
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Mitigation
PCBA Cleaning
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122
When to Clean?
Very high reliability applications
Medical, Military, Avionics, Industrial, Telecom
Sensitive circuitry
High-impedance circuits
High-frequency circuits
Operation in uncontrolled environments
Use of conformal coating
Concern over compatibility
Note: Some high-reliability markets have moved
away from cleaning
Automotive, Enterprise, etc.
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Industry Standards on PCBA Cleaning
Requirements driven by J-STD-001
Mandates 10ug/in2 (1.56 ug/cm2) for ROL0 or ROL1 (others based on limit established
by user)
Section 6.1
Assemblies should be cleaned after each soldering operation so that subsequent
placement and soldering operations are not impaired by contamination
Section 8.2.2
Cleanliness testing is not required (unless specified by the customer)
SPC not required (testing should be random, but sample plan not provided)
Minimum once every production shift
If any assembly fails, the entire lot shall be evaluated and re-cleaned and a random
sample of this lot and each lot cleaned since performing the last acceptable cleanliness
test shall be tested
Some guidance provided by two handbooks
Guidelines for Cleaning of Printed Boards and Assemblies, IPC-CH-65A (1999)
Aqueous Post Solder Cleaning Handbook, IPC-AC-62A (1996)
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Critical Aspects of PCBA Cleaning
Solder Paste / Flux Chemistry
Component Selection and Board Design
Equipment
Batch vs. Inline
Critical equipment parameters
Cleaning Solution
Includes solvent, chemistry, and temperature
Process Location
When to clean?
Cleanliness Requirements and Assessment
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125
J-STD-004 Flux Classification
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Whats Missing?
Minimal information on cleaning
Other than no-clean
Information needed
How to clean (cleaning solution, cleaning process)
What to clean (amount and type of residues)
Why no cleaning information?
Partially driven by process temperature, board design, and
board materials
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Missing Information (example)
Water Soluble is not equivalent to Water
Washable
Rosin-based flux residues can be removed by
water in combination with a saponifier
Non-water soluble flux residues can be removed
through impingement (residue is softened by
heated water and knocked off by force of
sprayed water striking the residue)
No-Clean can sometimes be cleaned
Sometimes, it can not
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Component Selection / Board Design
Challenges
High density
Low standoff
High density
Number of components per area
Number of tall / wide components
Low standoff components
Chip components (0402, 0603, etc.)
Area array components (BGA, CSP, etc.)
Bottom-terminated components (LGA, QFN, etc.)
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Chip Components
Some debate about worst-case
Larger components (e.g., 2512) have more surface area
Smaller components (0402, 0603) tend to have lower
standoffs (1-2 mil vs. 3-4 mil)
Potential design improvements for cleaning
No traces under components (most common)
Smaller bond pads (lifts up the component)
Thinner solder mask (increases standoff)
Components in parallel (prevents blocking of cleaning
solution)
Board cutouts (primarily for larger chip components)
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Area Array Components
Ball grid array (BGA) and chip scale
packages (CSP)
Standoff and ball-to-ball spacing shrinking
1.0 mm pitch = 20-25 mil standoff
0.4 mm pitch = 10-12 mil standoff
Limited design improvements available
Solutions more process-driven
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Bottom-Terminated Components
Components of greatest concern
Standoff similar to chip components; surface area similar to BGA
Fast growing component packaging
Current styles partially mitigated by thermal pad
Limited area under package to clean
Future versions problematic
Dual-row QFN (current standard is single-row)
Finer-pitch QFN (currently 0.4 mm)
Land grid array
Limited design improvements available
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QFN and Dendritic Growth
Large area, multi-I/O and low standoff can trap flux
under the QFN
Processes using no-clean flux should be requalified
Particular configuration could result in weak organic acid
concentrations above maximum (150 200 ug/in
2
)
Those processes not using no-clean flux will likely
experience dendritic growth without modification of
cleaning process
Changes in water temperature
Changes in saponifier
Changes to impingement jets
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Best Practices: PCBA Cleanliness
Confirm incoming PCB cleanliness
Clean after soldering operations
Control and measure
Water quality going into process
Assembly cleanliness
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134
Cleaning Equipment
Two options
In-line
Batch (dishwasher)
Batch tends to dominate
In-line primarily justified based on volumes
High-volume manufacturing tends to not clean
Ultrasonic
Rarely used on PCBAs
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Batch Cleaning Equipment
Motivations for batch cleaner
Insufficient volume for a dedicated line
PCBA is reasonably sized
Batch cleaner manufacturers
EMC Global Technologies
Aqueous Technologies
Manncorp
Austin-American
The batch cleaner should be capable of monitoring outflow
Aka, built-in cleanliness tester or resistivity monitoring
Alarm tends to be set to 4 to 7 megaohms
Closed loop can be a plus in low-cost countries
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Cleaning Process and Solution
Variables
Pure DI or Saponifier (type and concentration)
Temperature (120F to >175F)
Nozzle pressure
Agitation (spray in air)
Time
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Cleaning Process (cont.)
The majority of water cleanable solder pastes
have their residues removed by means of
heated (~120F - 135F/~53C 57C)
deionized water that is sprayed on to the
assembly at ~60 psi.
Temperature and pressure of the DI water
varies with each solder paste formulation, the
cleaning equipment and the angle at which
the water strikes the assembly.
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Process Location: Where to Clean?
One of the biggest variables in cleaning operations
Clean at the end
After all repair and rework
Clean twice
Once after standard assembly processes, once after
manual processes (e.g., repair and rework)
Can be driven by cleaning-sensitive components
Clean after every assembly process
Addresses concerns with density, flux compatibility
(heterogeneous contamination), and time sensitivity
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139
Mitigation
Conformal Coating
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Conformal Coating
The process of spraying a dielectric material onto a
device component to protect it from standing water,
fungus, dust, corrosion, abrasion, and other
environmental stresses
Coatings available include
Epoxy
Acrylic
Urethane/Polyurethane
Silicone
Fluoropolymers
Paralyene
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Conformal Coating Attributes
Easy to rework
Widely used
Low cost
Acceptable adhesion
Poor chemical resistance
High moisture resistance
Acrylic
No masking
Easy to rework
Moderate cost
Acceptable adhesion
High chemical resistance
Excellent moisture barrier
Fluoro-polymer
(Certonal)
Impossible to rework
Rarely used
Extremely high cost
Excellent adhesion
Excellent chemical resistance
Excellent moisture resistance
Paralyene
Possibility of rework
Moderate usage
High cost
Poor adhesion
Low chemical resistance
Excellent moisture resistance
Silicone
Difficult to rework
Widely used
Moderate cost
Good adhesion
High chemical resistance
Acceptable moisture barrier
Urethane
Difficult to rework
Sometimes needs compliant buffer
Not widely used
Good adhesion
Excellent chemical resistance
Acceptable moisture barrier
Epoxy
Comments Properties
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Conformal Coating Selection (cont.)
Major selection drivers
Cost
Temperature range
Glass transition temp (Tg)
Decomposition temperature
Ease of rework
Compatibility with supply chain
Prevention of migration (ECM) / corrosion is not
always the major focus
Acrylic dominates the market
Cheap, easy to apply, easy to rework, widely used
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Conformal Coating (cont.)
Does conformal coating prevent ECM?
Primarily against external contaminants (water, chemicals,
bugs, etc.)
Must adhere well to board surface and flux residues
Performance (in general)
Acrylic < Urethane < Silicone
Role of contaminants under coating critical
Physical objects (fibers, hair, etc.) can cause CAF type
failures
No-clean and other process contaminants can induce ECM
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Conformal Coating and No-Clean
Concerns about applying
conformal coating over no-clean
flux residues
Conformal coating suppliers tend to
not recommend
Some have compatibility docs
Residues can reduce adhesion,
potentially resulting in
delamination
Creates micro-condensation
conditions; more detrimental than no
conformal coating
Has not stopped the practice
Current industry standards create
relatively benign conditions
Allows products to pass qualification
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Conformal and No-Clean (cont.)
Work by Mensah and Hunt
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146
Qualifying Conformal Coatings
The primary industry document for qualifying
conformal coatings is IPC-CC-830B
Qualification and Performance of Electrical Insulation
Compound for Printed Wiring Assemblies
This document has one major limitation for OEMs
It is designed for qualifying conformal coatings separate from
the manufacturing process
Therefore, it is not an appropriate document for
gauging interactions between no-clean flux residues
and conformal coating
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Qualification (cont.)
There are two basic test methodologies to
assess compatibility of conformal coating with
no-clean flux residues
Adhesion
Electrochemical migration (ECM) /
surface insulation resistance (SIR)
Adhesion can be characterized through
Surface energy
Peel tape tests
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Adhesion: Surface Energy
Surface energy can be
characterized through the use
of dyne pens
Contains solution with calibrated
surface tension (30 dynes/cm to
44 dynes/cm)
If solution does not bead up, try pen with higher surface
tension
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149
Adhesion: Peel Tape Test
Two peel tape tests are typically
performed in the electronics industry
IPC TM-650 2.4.1.6
Adhesion, Polymer Coating
ASTM D 3359
Measuring Adhesion by Tape Test
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150
Peel Tape Test: IPC
The IPC test involves a square pattern
(IPC-B-25A)
Peel test at initial and after
3 hours at boiling; rating system
based on amount of peeling
More typical for solder mask then
conformal coating
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151
Peel Tape Test: ASTM
Two test methods: Method A and Method B
Method A: Cross-Cut X / Method B: Cross Cut
Method A is typically performed on films
greater than 130 m (5 mils) and wood substrates
Method B is typically performed on films
less than 130 mm (5 mils) and metal substrates
Method B can be used on films greater than 130 um is allowed if
wider spaced cuts are employed.
A lattice pattern is scratched into the coated surface with six or
seven lines in each direction.
Any loose fragments are brushed away.
The ASTM qualified tape is pressed firmly to that area.
Within 30 to 90 s, the tape is pulled back at a 180angle.
Adhesion is ranked based on a scoring system
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Adhesion Scoring System
ASTM D 3359, Test Method A, X-cut tape test (wood substrates)
5A - No peeling or removal of film along incisions
4A - Trace peeling or film removal along incisions or at intersection
3A - Jagged removal along incisions up to 1.6mm (1/16 in.) on either side
2A - Jagged removal along most of incisions up to 3.2mm (1/8 in.) on either side
1A - Removal from most of the area of the X incisions under the tape
0A Removal beyond the area of the X incisions
ASTM D 3359, Test Method B, Cross-cut tape test (metal substrates)
5B The edges of the cuts are completely smooth and none of the squares of film in lattice have
been detached.
4B Small flakes of the coating are detached at the lattice intersections. Less then 5% of the lattice
area is affected.
3B Small flakes of the coating are detached along the edges and at the intersections of the cuts.
The area affected is 5 to 15%.
2B The coating has flaked along the edges of the cuts and on parts of the squares. The area
affected is 15 to 35%.
1B The coating has flaked along the edges of the cuts in large ribbons and whole squares have
been detached. The area affected is 35 to 65% of the lattice.
0B Flaking and film detachment is greater than 65% of lattice area.
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Peel Tape Testing: Summary
Perform test after some exposure to
temperature and humidity? No
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Qualification
Cleanliness and Conformal Coating
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Qualifying Chemistries and Cleaning
Option 1: Test Vehicle
Typically used for materials qualification
Option 2: Actual Product
Part of product qualification
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Test Vehicle Qualification
Fabricate from same material as production unit
(board, solder mask, solder, flux)
Use of dummy parts and comb patterns
Consider IPC B-52
Can be modified to mimic existing designs and process
Ensure minimum of two structures
Smallest spacing at relevant voltage
Highest electric field at relevant spacing
Can clean test vehicle before use if relevant
Assesses materials and cleaning interaction (not board
contamination)
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IPC-B-52 (IEC TB-57)
The latest generation of test coupons
Similar to designs from NPL, Rockwell Collins, & IBM
Main SIR Test Board
IC Test Coupon
Solder Mask Adhesion
SIR mini-coupons
Packages
0402 1206
QFP (no 0.4mm pitch)
SOICs and BGAs
Through-Hole Header
Comb patterns (5 mil)

Not specifically called out in any TM-650 test method
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Current SIR Test Standards
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Recommended Test Method
Flux application and preconditioning
Solder paste / Wave solder / Rework
Clean
Exposure to mild temperature and maximum
humidity without condensation
35 to 40C / 93%RH
72 to 120 hours of exposure
Continuous monitoring (1 second per reading)
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Product Qualification
Consider testing entire product, if resource- or time-limited
40C/93%RH for 72 to 120 hours
Extend time period if using conformal coating or potting material
Do not test at 85C/85%RH for dendritic growth (surface ECM)
Some issues with CAF as well
Study by Sohm and Ray (Bell Labs) demonstrated degradation of
weak organic acid residues above ~55C
Reduces their effect on surface insulation resistance
Turbini (Georgia Tech) demonstrated breakdown of polyglycols
at elevated temperature as well
Absorption into board can increase risk of CAF
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161
Case Study 1
Appliance controls
manufacturer
Use of reverse auction
First exposure to East
Asia board manufacturer
Elevated rate of field
failures (5-15%)
Large number no trouble
found (NTF)
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162
Case Study 1 (cont.)
1 Bare PCB
2 After through hole placement
3 After SMT placement
4 After wave solder
5 Before conformal coating
6 After conformal coating
7 After final inspection

0
5
10
15
20
25
30
0 1 2 3 4 5 6 7 8
Process Steps
C
o
n
t
a
m
i
n
a
t
i
o
n

L
e
v
e
l
s

(
g
/
i
n
2
)
Cl
Br
Elevated chloride and bromide levels
Board manufacturer using city water to rinse boards before solder mask
Elevated temps to cure coating induced diffusion of trapped contaminants
Ion chromatography (IC) capability; No IC requested; no IC performed
2004 - 2007
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163
Case Study 2
Failure of resistor networks
in field
16 leaded SOP
Controlled office
TtF: Days to months
Cross-sectioning identified
popcorning
Rated MSL 1
Pb-free reflow
Internal delamination
Induced migration between
metallic elements
2004 - 2007
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164
Case Study 3
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165
Case Study 4
Automotive module subjected
to frost test (moisture
susceptibility)
Soaked at -20C for 2 hours.
Transfered to 45C/95-100%RH
in less than 1 min.
Functional/parametric tests
performed at 5, 30 and 120
minutes
Dendritic growth observed on
several ceramic chip capacitors
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Case Study 4 (cont.)
Multiple root causes
Capacitors located adjacent to
holes and cut outs in housing
Created ducting condition for
condensation on cold board
Excessive flux residue from wave
soldering process
Previous designs
Conformally coated
No wave soldering (paste in hole)
Cleaned
Failure mode was intermittent
Design verification vehicle passed
Product verification vehicle failed
Both had dendrites!
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Case Study 5
Avionics system
Failure during test
Conformal coating on the top
extended down the sides of
the package
Did not cover the leads, seals,
or the package bottom
Residual RMA solder flux
identified
Vapor degreasing process did
not reach under component
Pin to case resistance of 140
k
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Case Study 6
Red phosphorus flame
retardant
Reaction with moisture to
form phosphorus-based
acids
Minimum moisture content
required (~80 to 85%RH)
Additional process
chemicals can weaken
silica-epoxy bond
Failure behavior
Initially intermittent
Permanent over time
0.00
0.05
0.10
0.15
0.20
0.25
0 5 10 15 20 25 30 35
Time
1/2
(hour
1/2
)
M
o
i
s
t
u
r
e

C
o
n
t
e
n
t

(
%
)
85
o
C/85%RH
40
o
C/93%RH
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169
Case Study 7
Migration over the conformal coating
Condensation observed on chamber
walls during temp cycling.
Chloride concentration of 11 ppm.
Drinking water typically 6 to 20 ppm
IC found nominal levels of chloride
on board (2 to 3 micrograms/square
inch)
Cyclic condensation can lead to
wearout type behavior
Initial condensation weakens by
inducing dissolution
conductor material
Elevated presence
of metals eventually
induces ECM
between insulated
conductors.
Location Customer DfR Solutions
Sensor Sensor A Sensor B Sensor C Sensor D
Trial 1 2 1 2 1 2 3 4 1 2 3 4
F (g/in
2
) < 0.1 < 0.1 < 0.1 < 0.1 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01
Cl (g/in
2
) < 0.1 < 0.1 3.73 4.76 2.91 2.86 2.93 2.93 3.26 3.40 3.29 3.35
Br (g/in
2
) < 0.1 < 0.1 < 0.1 < 0.1 0.55 0.50 0.50 0.50 0.57 0.61 0.59 0.59
NO
3
(g/in
2
) < 0.1 < 0.1 < 0.1 < 0.1 1.08 1.02 1.04 1.06 1.34 1.36 1.41 1.41
PO
4
(g/in
2
) < 0.1 < 0.1 37.3 33.8 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01
SO
4
(g/in
2
) < 0.1 < 0.1 < 0.1 < 0.1 0.61 0.55 0.55 0.55 0.73 0.73 0.73 0.75
NO
2
(g/in
2
) N/A N/A N/A N/A < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01
Acetate (g/in
2
) < 0.1 < 0.1 < 0.1 < 0.1 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01

2004 - 2007
Phone (301) 474-0607 Fax (240) 757-0053
2004 - 2009
170
Conclusion
Contamination and Cleanliness requirements should
be clearly detailed to the supply chain
PCB
PCBA
LCD
Etc.
Cleanliness should be validated
Materials compatibility (test coupon)
Product qualification
Ongoing cleanliness assessment (IC)
2004 - 2007
Phone (301) 474-0607 Fax (240) 757-0053
2004 - 2009
171
Any Questions?
2004 - 2007
Phone (301) 474-0607 Fax (240) 757-0053
2004 - 2009
172
Drivers for ECM
Electrolytic solution
Moisture
Temperature
Humidity
Cracks
Contamination
Ions
Contamination
Cleanliness
Electric field
Voltage
Spacing
Insulation
Solder mask
Encapsulant
Ceramic
Conductors
Metal alloy
Movement of metal through an electrolytic solution
under an applied electric field between insulated
conductors

Contamination and Cleanliness IMAPS 2010 06

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Contamination and Cleanliness IMAPS 2010 06

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Craig Hillman

Contamination and Cleanliness

Halides are not required to induce dissolution

= metal ion concentration

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