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PHOTEC
Dry Film Photoresists
Technical Process Guide

Troubleshooting Guide

Enthone
www.cooksonelectronics.com
Issued: 11/02
Supercedes: 10/99
2002 Enthone Inc.
TPG-Photec: Europe

*Trademark used under license from Hitachi Chemical Co., Ltd.

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PHOTEC*
Dry Film Photoresists
Table of Contents
Section

Pages

Introduction

2-3

Technology

4-9

Substrate Preparation

10-22

Lamination

23-28

Exposure

29-33

Development

34-41

Etching

42-50

Resist Stripping

51-53

Questions and Anwers

54-62

Appendices

63-73

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PHOTEC*
Dry Film Photoresists

Introduction

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INTRODUCTION
This technical process guide will provide detailed instruction in the use and
application of PHOTEC* dry film photoresists, as well an overview on resist
technology.
Historical Background
Dry film photoresists (resists) were first patented in 1968 by Mr J Celeste of
DUPONT. Since that time they have been used extensively in the primary
image formation on printed wiring boards.
At the time of introduction dry film resists were processed with solvents. It was
not until the mid 1970s that the aqueous (water-based) processing was
introduced.
Hitachi Chemical creates the resists. Enthone delivers the results.
As noted by the table below, Hitachi Chemical Co., Ltd. has been a leader in
dry film resists for 25 years.
1974
1975
1985

First PHOTEC products released in Japan

First aqueous PHOTEC product released
PHOTEC released to Europe

In 1985, Enthone and Hitachi Chemical Company, Ltd., formed a strong

partnership. For fifteen years, Enthone has been the exclusive distributor and
marketer of PHOTEC dry film resists throughout Europe. Backed by
unmatched technical support, PHOTEC dry film rolls are custom slit at
Enthones ISO 14001 certified facility in The Netherlands.
The dry film resist as supplied consists of a three-layer construction. The
resist is supported on a polyester film and protected on the other side by a
polyethylene-separating layer. This polyethylene-separating layer, which is
removed prior to use, is so that it can be rolled ready for application by the
laminator. Polyester is used as the support film for two reasons:

It has good mechanical and thermal properties so that there is no

distortion or wrinkling when heat and tension is applied at the
lamination stage.

Polyester has low permeability to oxygen. If oxygen were to permeate

through this protective layer to the resist in the unexposed state, free
radicals could be generated which would lead to polymerisation of the
resist.

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PHOTEC*
Dry Film Photoresists

Technology
Acrylic Polymer
Reactive Monomer
Imaging Agent
Photo sensitisers and Photo initiators
Resist: General Formulation Principles

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TECHNOLOGY
A dry film photoresist is a complex mixture of components, each having a very
important role in the function of the resist. A typical dry film resist contains:

Acrylic Polymer
Photo-reactive monomer
Photo sensitisers
Photo initiators
Imaging agent
Fillers and adhesion promoters
Plasticisers, etc.

Dry Film Resist Component

Properties

Acrylic Oligomer (Monomer)

Resolution
Resist Profile
Sensitivity
Stripping (Size of stripped flake)
Resist Profile
Sensitivity
Resolution
Latent Image (Contrast)

Adhesion
Resist stability

Photoinitiator

Imaging Reagent
Additives

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Acrylic Polymer (Binder Polymer)

The polymer is the backbone of the resist and gives physical strength to the
resist. The main chemical composition is a copolymer of acrylic or methacrylic
esters with acrylic or methacrylic acid. The molecular weight of the polymer is
a maximum of 250,000.
H
H
H
H
I
I
I
I
- CH2 C CH2 C CH2 C CH2 C
I
I
I
I
O
CO
CO
CO
I
I
I
I
OR
OH
OR
OH

R =Alkyl group
n= Polymer chain length
The ratio COOH groups to the alkyl groups determines the ease of
development and stripping. It will also determine the chemical resistance and
in particular the resistance to alkaline etchants.
The carboxylic groups within the polymer chain will react with either Sodium
Hydroxide (NaOH) or Potassium Hydroxide (KOH) to make the polymer
water-soluble. Hence, the nomenclature aqueous type resist.
Reactive Monomer (Oligomer)
The monomers may be a mixture of mono or polyfunctional acrylates. The
molecular weight of the monomer will affect the odour of the resist, the rate of
polymerisation (i.e. the speed of exposure), and other physical properties of
the resist.
These monomers are dispersed within the binder polymer mixture such that
when the reaction takes place it forms a highly interconnected three
dimensional network of polymers. This then forms a very strong and flexible
resist.
After exposure up to 30-40 % of this monomer is left unpolymerised. In certain
cases this may form stickiness of the resist after development and if the
panels are stacked on top of each other they may stick together.

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Imaging Agent
The blue or green colours are the most commonly used colours as the
unaided eye judges these to provide the best contrast to the pinkish colour of
the copper surface. Normally a triarylmethane dye such as Crystal Violet or
Malachite green is used. These products are used in the resist formulation in
their Leuco or white form.
The Leuco form oxidises when exposed to ultraviolet radiation to form a
coloured compound and gives the printout image which is essential in
assuring correct registration of the phototool to the drilled holes.
Dyes that provide a latent image when exposed are referred to as photochromic. These dyes must have a low absorption of light in the spectral range
of sensitivity of the dry film in order not to reduce the radiation energy
available for resist polymerisation. In some formulation of resists the dyes
used work with a synergistic effect to help initiate the resist polymerisation
through electron transfer mechanism. Dyes of this form include xanthene and
acridinium compounds. The peak spectral absorbency of PHOTEC dry film
resist is 365 nano-metre.
Photo sensitisers and Photo Initiators
In order to polymerise the photoresist must contain some light sensitive
molecules that are able to convert the absorbed energy into a form that
enables the functional monomers to polymerise.
There are two basic types of photoreactive chemicals used in photoresists.
Photo sensitiser: The photo sensitiser absorbs the energy and
transfers it to another molecule, which forms the primary reactive
component. The photo sensitiser is not consumed or structurally
altered and could be considered a photo catalyst.
Photo initiator: A photo initiator is the additive present which
facilitates the initiation reaction. In the case of PHOTEC, the photo
initiator absorbs the radiation emitted by the high pressure mercury
lamp or light in the wavelength of about 365 N.M. and then changes to
form the reactive species - "free radicals". The photo initiator is
consumed in the polymerisation reaction.

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Mercury lamps were the first types of lamps to be used in exposure systems.
The wavelength of 365 N.M. was originally used because it is the principal
emission of the lamp. Molecules known to respond to radiation of this
wavelength are of many structures and numerous variations. However, the
molecules in common commercial use are relatively few. This is because
some of the important considerations for obtaining efficient photo initiation are
wave length sensitivity, relative absorption coefficients, quantum yields, other
reacting species and any side reaction products that do not stop
polymerisation. Typical molecules that are used include:
4,4' Bis (Dimethylamino) bezophenone (Michlers Ketone)
N- aryl - - amino acids
Phenyl imidazolyl dimers
Benzophenone derivatives (no longer used)

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Resist: General Formulation Principles

Increase resolution by
Reducing the molecular weight of polymer.
Increasing the number of carboxylic acid groups on the polymer
chain.

Enhance resist adhesion and provide a wider operating window by

Increasing the glass transition temperature (Tg) of polymer.
Increasing the cross-link density at polymerisation.
Increase conformance by
Decreasing molecular weight of polymer.
Low contamination in the electrolytic solutions and a smaller resist foot, is
achieved by
Decreasing molecular weight of polymer.

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PHOTEC*
Dry Film Photoresists

Substrate Preparation
Drilling
Deburring
General
Base Copper Laminate
Electroless Copper
Electro Deposited Copper
Direct Metallisation
Base Copper Laminate
Electroless Copper
Electro-deposited Copper
Direct Metallisation
Pretreatment Methods
Abrasive Brush
Brush Pressure, Brush Footprint
Surface Condition of Brushes
Water Placement onto Brushes
Pumice Brush
Spray Pumice
Chemical Clean

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SUBSTRATE PREPARATION
Prior to the final surface preparation and lamination, drilling and deburring
may impact the properties of the dry film resist.

DRILLING
Burrs or holes with jagged edges are caused by drilling and may effect the
tenting property of the resist. Burrs are caused by three major factors:

An incorrect drill speed/feed ratio. (The penetration of the drill into the
base material is too fast for the speed of rotation of the drill bit.)
The drill bits are not sharp or have chips in the cutting edges.
Choice of the wrong type of support board on the exit side of the drill
stack.

DEBURRING
Deburring is an operation that is necessary when the drilling operation lacks
complete control.
Deburring is a mechanical operation. If not carefully controlled, deburring may
cause deep scratches on the substrates surface and lead to resist
conformance issues. The periphery of a drilled hole may be damaged giving a
dish down on one side of the hole that may lead to conformance or tenting
breakdown.
Substrate preparation is a critical stage prior to the lamination of the
photoresist. The photoresist requires a clean micro roughened surface with a
high surface energy in order to obtain good adhesion. Unless the copper
surface is correctly prepared, there is a great potential for poor photoresist
adhesion.
Mechanical and chemical bonding are two adhesion mechanisms that are
important in obtaining the optimum properties of the resist. Immediately after
lamination the initial adhesion mechanism is mechanical; after about five
minutes the resist starts to form a chemical bond.
PHOTEC resists experience a covalent chemical bond that is formed between
a hydrogen atom from the acrylate and the clean copper surface. There are
resists on the market that contain either a sulphur or nitrogen compound to
increase the adhesive forces. In the case of sulphur compound compounds
such as benzotriazole are used.

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To obtain the ideal adhesion values of the dry film resist to the substrate, a
three dimensional, highly micro roughened surface must be generated during
the pre-cleaning process. This surface allows for the maximum number of
anchorage points required for mechanical interlocking of the photoresist to the
copper substrate. The surface must have a high surface energy for the correct
chemical bond to form between the resist and the substrate.
Checks should be made after pretreatment to ensure that the prepared
surface supports a film of water for at least 30 seconds. This is also known as
the water break test, as failure to hold the water on the surface indicates that
oils or grease remain and should be cleaned. Good water rinsing and drying
after the pretreatment operation is essential. This will ensure complete
removal of any chemical, pumice or copper dust left on the surface and in the
holes. If water remains in the holes during lamination this water tends to form
steam which can cause a pressure build-up in the hole resulting in
subsequent tent failures.
The pH of the water used for rinsing should be controlled so that it is either
neutral or very slightly acidic, pH 6-7. Dry film adhesion is affected by the
surface pH of the substrate. An alkaline surface will give rise to less adhesion
forces and may result in lifting of the resist. A slightly acidic surface gives
ideal adhesion forces. If the substrate surface is too acidic then resist lock-in
may possibly occur.

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GENERAL

All panels should be free from grease, oil, fingerprints and uncontrolled
oxidation. Panels should be handled using clean, lint-free gloves that are
changed regularly. (See Appendix 3 for specification of panel surface.)
There are basically four types of copper surfaces that are used in circuit
formation.
Base copper laminate
Electroless copper
Electro deposited copper
Direct metallisation
Base Copper Laminate
A base copper laminate is an electro deposited copper foil that has been
deposited without additives and therefore the crystal structure of the copper is
columnar. The surface is protected from oxidation by an anti-tarnish, usually a
chromate layer.
Electroless Copper
Electroless copper is normally fine grained but is dependent on the
complexing agent used in the chemical formulation of the deposition process.
Electro Deposited Copper
Electro deposited copper is either a lockin plate of about 5 microns in
thickness or a full deposit of about 2530 microns. These deposits can be
either fine grained equiaxed or lamellar in structure dependent on the
chemical composition of the deposition process and the equipment used for
electro deposition. Electro deposition processes are available to deposit finegrained matte deposits which are ideal for direct lamination of dry film resists.
Direct Metallisation
The surface characteristics are dependent upon the direct metallisation
process being used. There are several different types of direct metallisation,
including:
Conductive Polymer
Carbon or Graphite
Palladium Chloride
Palladium Sulphide

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BASE COPPER LAMINATE
Base copper laminate is used for innerlayers of multilayer and single-sided
boards or double-sided non-plated through boards. As delivered, the copper
foil is often protected by a chromate or zinc passivation to prevent copper
oxidation. To obtain optimum adhesion this passivation film must be
completely removed.
Accepted pretreatment methods include:
Abrasive Brush
Pumice Brush
Spray Pumice
Acid clean
Chemical clean followed by
cleaner/microetch.

microetch

or

combined

Care should be taken since the thickness of the substrate may be as low as
0,1mm. Any bending or creasing of the substrate will give rise to rejects due
to poor conformance of the dry film at the lamination stage.
The pretreatment method should also take into consideration the possible
stretching of the substrate under the influence of mechanical stresses
produced by abrasive brushing etc. Any stretching of the substrate will give
registration problems at the exposure stage. (See Section on pretreatment
methods for guidance on these processes.)
Electroless Copper
The type of electroless copper process will influence the adhesion of the
photoresist. It will also depend upon whether anti-tarnish is used after the
electroless copper.
In general, surfaces with EDTA-based electroless coppers are somewhat
more difficult to achieve good post-lamination adhesion than Quadrol-based
(Ethylene dinitrilo-tetra-2 propanol) electroless coppers. This is due to the
different crystal structures obtained from the two different processes. The
EDTA-based process provides a finer grained, higher crystal density
structure.
In many electroless copper processing lines an anti-tarnish stage is used to
prevent unwanted oxidation of the copper. Alkaline anti-tarnish formulations
have a tendency to provide worse adhesion of the photoresist than those
based on mineral or organic acids. This is due to the fact that resists adhere
better to a slightly acid surface than an alkaline surface, even after thorough
rinsing the surface pH may follow the pH of the last processing stage.
Although dry film resists will adhere to an electroless copper surface it is
normal for these surfaces to be either pumice brushed or chemically treated
prior to resist lamination.

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ELECTRO DEPOSITED COPPER

If either full panel plating or lock in plate is carried out prior to lamination
three problem areas have been identified.

Uneven deposit (i.e. greater deposit thickness in the high current

density areas), provides unequal pressure across the board at the
lamination stage, resulting in poor adhesion in the centre of the panel.

Unless the boards are pre-treated effectively prior to lamination the

surfaces may be too smooth to obtain good initial, post lamination
adhesion.

Under exceptional circumstances the electrolytic copper deposit may

contain a high concentration of grain refining additives.

Grain refining additives contain sulphur and nitrogen compounds similar to

those used in certain dry film resists imparting adhesion to the substrate. The
electrolytic copper additives may give rise to two side effects.

The high concentration of additives may interfere with the resist-tosubstrate adhesion mechanism.

The additives may chemically bond with the dry film resist and increase
the adhesion to such an extent that stripping of the resist may become
a problem.

The pretreatment used for these panels must take the above points into
consideration.

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DIRECT METALLISATION
Each type of direct metallisation requires different pretreatment methods.
Carbon and graphite processes require that the carbon or graphite be
removed by an aggressive microetch and the surface protected by an organic
anti-tarnish prior to resist lamination. Unless the carbon or graphite is
completely removed, resist adhesion failures may occur. (Note: Carbon
products are used as lubricants in other industries.) The anti-tarnish normally
based on benzotriazole is used not only to prevent oxidation of the copper
after the microetch but also to assist with adhesion of the photoresist.
As its final chemical stage in the metallisation sequence palladium sulphidebased processes include a microetch which removes the palladium sulphide
from the copper surfaces. Therefore, it is essential that no additional etching
or mechanical methods are used in the pretreatment process prior to
lamination. Additional microetching may cause ring voids at the final copper
electrodeposition stage.
Conductive Polymer
The surfaces that have been treated with direct metallisation using a
conductive polymer, do not normally require more surface preparation other
than a chemical clean prior to lamination. If, however, the surface is oxidised it
may be treated with a combined cleaner/microetch. The conductive polymer is
only adherent to the dielectric substrate and not the copper surfaces.
Therefore, the copper surfaces may be microetched with no problems.

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PRETREATMENT METHODS
The four major methods used for surface preparation require different
equipment. Although each method provides the basic requirement for resist
adhesion, each yields different surface topography that may affect the final
circuit requirements.
Abrasive Brush
The abrasive brush is one of the oldest methods of cleaning copper prior to
resist application. It is a simple method that uses a rotating abrasive brush to
mechanically remove oxides from the copper surface. However, successful
pretreatment requires that the following control parameters be taken into
consideration.

Grade of abrasive used for the brush

Brush pressure and the resulting brush footprint
Surface condition of the brush
Placement of water spray onto the brush

Abrasive brushes are by definition brushes that remove surface imperfections

and the base copper by mechanical means. The result is that the surface of
the copper will be degraded to an extent that depends on the grade of
abrasive used. Abrasives used in the brush manufacture are normally based
on silicon carbide that has excellent abrading power and long life. To obtain
the surface finish required for resist application, the particle size of the silicon
carbide must be chosen carefully.
To achieve good resist conformance, a controlled surface topography is
required. This enables excellent adhesion without problems of nonconformance.
The grades of brush recommended are a combination of brushes with two
different particle sizes. For the first stage it is recommended that a 320 grit
size is used to remove all oxides, surface imperfections etc., followed by a
600 or 800 grit brush to smooth the surface to the final roughness
recommendations.
By removing surface imperfections, a surface finish with controlled
topography is provided with a surface energy that enables the resist to have
initially good mechanical adhesion. The resist may then form a chemical bond
to the surface.

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Brush Pressure, Brush Footprint

The actual pressure applied to the brushes is dependent on the thickness of
the panel and also the width of this panel. The pressure is normally controlled
by a torque metre fitted to the motor that turns the brush. Actual pressure
applied is normally controlled by the brush footprint, which is set at between
10 and 15 mm. This brush footprint is the area of the brush that is in contact
with the surface of the panel at any time.
Surface Condition of Brushes
The brushes will wear with the number of panels processed and must be
inspected for evenness of wear. It is recommended to position the panels
alternatively across the total length of the brush to ensure even wear over the
brush. If this is not carried out then uneven wear will result in a possible
pretreatment difference across the panel being processed.
Although copper is considered a relatively soft metal it becomes much harder
as it is subjected to mechanical forces. Any copper particles that remain in the
surface of the brush will result in a deep scratch in the panel being processed.
Water Placement onto Brushes
During use the brushes are sprayed with water to both keep the temperature
constant and to remove copper particles from the surface. It is essential that
the water be sprayed onto the surface of the panel at the point where the
actual brushing action takes place.

Abrasive Brush Pretreatment

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Pumice Brush
Pumice brush is a means of cleaning a copper surface by using a suspension
of pumice in water which is brushed onto the surface by means of a nylon
brush. If properly controlled, it does give a three-dimensional structure on the
copper surface that is suitable for resist application.
The pumice brush stage may be one of three different combinations.
Specifically, there are three abrasive media that are used in combination with
a nylon brush: normal pumice, white pumice, and an aluminium oxide that is
used as a replacement to pumice. Normal pumice is a grey/cream colour and
comes in various particle sizes. Typically 3 ON grade are used but this can
vary between ON and 6N.
Pumice is a natural ore product that is ground and sieved with different mesh
sizes to produce the different products. Due to the fact that it is a natural
product, the particles are of random shape and with different angular
configuration. It must be noted that the grade of pumice is normally controlled
by passing through different sieve sizes. Checks should be made to
determine the minimum particle size and concentration contained in the
available product. A high concentration of small particles does not give the
required surface topography.
Pumice is relatively soft and during use the angular shapes are converted to a
rounded structure. Changes in angular structure impacts its effectiveness as
an abrasive medium. The action of the brushes with the abrasive particles
remove any inorganic contamination from the copper surface and leaves the
copper in an active state with a surface that is ideal for resist lamination.
In practice pumice is used in 1218 % weight/volume pumice-to-water ratio.
This pumice concentration must be checked at least every working shift and
adjusted if necessary to the correct concentration. Since copper is removed
during the brush/pumice operation, the copper concentration in the pumice
increases with use. This copper concentration must be controlled and the
pumice changed regularly to ensure constant quality. Commercial equipment
is available to reduce the copper particles in the pumice mixture.
The white pumice or B grade is a harder material with a more consistent
particle size.
Pumice in a particle form may be trapped in through-holes. This entrapped
pumice must be removed by either high pressure water rinsing or by the use
of ultrasonics. It must be remembered that high-pressure water is only
effective on the surface of the panel, actual pressure of the water in any
through-hole is much lower than the force on the surface.
If pumice brush is used it is essential to remove all particulate matter from the
panel surface prior to lamination otherwise conformance of the resist will
result. Poor resist conformance will give rise to either open or short circuits
dependent on which part of the circuit the pumice particle is trapped or the
different type of circuit produced.

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As with all mechanical methods, only inorganic contaminants will be removed

from the copper surface. The method will not remove oils or grease from the
surface.
Aluminium oxide is an ideal replacement for pumice. It is harder with a more
angular particle. Being harder it has a longer working life. The major
drawback, however, is that aluminium oxide is more expensive and does give
more wear on the equipment. Spray nozzles must be changed to allow this
material to be used. The same guidelines presented for pumice should be
noted for aluminium oxide.

Pumice Brush Pretreatment

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Spray Pumice
Spray pumice a common method used in the PWB industry. The method
employs pumice that is sprayed under pressure onto the copper surface. The
mechanical action of the pumice under pressure removes all inorganic
impurities and also copper from the surface. Nozzles must be checked to
ensure even application of the pumice over the entire surface otherwise resist
adhesion may become a problem. All guidelines presented for the
pumice/brush operation should be followed for the spray pumice.

Chemical Clean
Provided that the chemistry is well controlled, the chemical cleaning method is
the preferred method of cleaning the copper surface prior to resist application.
This method eliminates the possibility of particulate matter on the surface
which may become entrapped under the laminated resist.
There are two different chemical cleaning options:

A two-stage process (cleaner, followed by microetch)

A combined cleaner/microetch

Either option will achieve a clean micro-roughened surface.

The thickness of copper removed during the etching process must be
controlled for consistent performance. Although the actual amount of copper
removed during processing is dependent on the process chemistry, it is
normal to remove about 0,61,0 micron of copper. Technical data supplied
from the process supplier must be observed for optimum surface topography.
The temperature of the process and the dissolved copper content determines
the actual crystal structure of the copper surface. As the copper concentration
increases in the microetch, the crystal structure changes from an angular
structure to a more polished rounded crystal structure. It is the angular form of
the crystal that is required for optimum resist adhesion. Good water rinsing is
required to remove all chemical products from the surface before drying and
resist application.
In practice there are three different oxidising chemicals used for the microetch

Hydrogen peroxide
Sodium or potassium persulphate
Sodium or potassium monopersulphate

Hydrogen peroxide is the least expensive material and has the highest weight
per volume of oxidising power, however unless carefully controlled it does not
produce the ideal crystal structure. Various additives are available to control
the stability of the hydrogen peroxide and each may have different effects on
the crystal structure produced.

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Normal persulphate is the most commonly used material for the microetch
formulation. However, monopersulphate is preferred for the ideal surface
topography.

Chemical Clean Pretreatment

Both spray pumice and cleaner/microetch preparation prior to resist

application produces a homogeneous three-dimensional microroughend
surface. For high density fine line circuitry a properly controlled chemical
cleaning method is the preferred method of pretreatment since it does
eliminate the possibility of particulate matter from the copper surface.

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PHOTEC*
Dry Film Photoresists

Lamination
Preheat Temperature
Rollers
LaminatingTemperature
Pressure
Speed
Hold Time after Lamination

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PHOTEC*
Dry Film Photoresists

Lamination

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LAMINATION
Lamination is the application of the dry film resist to a properly prepared
substrate.
The lamination process must be carefully controlled to ensure that the
required mechanical adhesion of the resist to the substrate is obtained by
flowing the resist into the surface irregularities. The resist should not flow too
much into any drilled holes or slots. Over flowing of the resist will cause
thinning along the periphery of holes and result in tent breakage. Therefore, a
correct balance of all the lamination parameters is crucial to ensure optimum
performance of the resist.
There are different types of proprietary laminators on the market ranging from
manual to fully automatic and from hot rollers being heated by resistance
heaters within the roller to indirect heating of the rollers by infrared. In all
cases the recommendations of the manufacturer must be followed. The basic
principle of the operation is to preheat the resist to a temperature of 110 +/100C to lower the viscosity of the resist just prior to application, under
pressure, to the substrate.
A normal sequence of operation is: Preheat substrate (40-500C)
Heat photoresist (110 +/- 100C)
Apply resist by roller pressure to the substrate. Typically a
pressure of 2-4 Kgf/cm2 is applied.
Lamination speed 1,0-3,0 meters per minute
Although preheating the substrate is not essential, it does ensure that the cold
substrate does not act as a heat sink and thus reduce the actual temperature
of resist at the lamination stage. If it were to do so it would affect the adhesion
and conformance of the resist to the substrate.
There must be a correct balance of lamination temperature, pressure speed
and resist tension to ensure that maximum resist adhesion and tenting ability
from the photoresist is obtained.
During lamination the resist is heated on one side and is laminated onto the
cooler substrate surface, thus a temperature gradient exists through the
resist. The lower molecular weight and lower boiling point fraction of the
chemicals within the resist will migrate to the cooler surfaces. A hold time after
lamination prior to further processing is to ensure that mobile chemicals
equilibrate with the higher molecular weight fraction.

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Preheat Temperature
The actual preheat temperature required is dependent upon both the
thickness of the dielectric and the copper on the surface. As the thickness of
either or both increase, the greater the thermal heat sink. In order to obtain a
surface temperature of 40500C, the preheat temperature must be adjusted
accordingly.
If the preheat temperature is too over 550C, wrinkles may occur during
lamination. When using an automatic cut sheet laminator, wrinkling is
particularly predominant at the edges of the panel. Thinning of the resist at the
periphery of holes or slots can occur if lamination speed is too low or the
lamination pressure too high.
If the preheat temperature is too low poor resist adhesion immediately after
lamination will result. Resist conformity to the substrate, especially in deep
and narrow areas, will be imperfect at best.
Rollers
The condition of the rubber on the rollers is important to ensure a constant
pressure over the entire panel. Any imperfections in or on the surface will
appear as defects on the laminated resist. A cut or a piece of rubber removed
from the roller will give a lower pressure at that spot during lamination and will
in severe cases show up as a blister on the surface of the laminated resist.
The hardness of the rubber should be about 65 Shore hardness. If it is harder
than this then the resist will be pushed into the holes or slots on the panel. If
the hardness is too soft poor conformance will result. The thickness of rubber
on the rollers should be as recommended by the equipment manufacturer.
Care should be taken when re-coating any rollers since the removal of the
rubber is normally mechanical and at this stage the steel shaft is reduced in
diameter. To obtain the required outside diameter of the roller, a thicker
rubber will be applied. Rubber is a poor conductor of heat and therefore, the
actual transfer of heat from the heating elements inside the roller will be less
than normal.
During lamination of a batch of boards the roller may not be able to maintain
the correct lamination temperature. On most laminators the heating is
accomplished by a resistance heater located within the steel core of the roller.
To ensure that the heat is transferred from this element to the actual roller a
heat transfer gel is used. Unless this gel is evenly coated around the heating
element, irregular heat transfer will occur along the length of the core and
around the diameter. All rollers should be checked whenever they are
changed and also on a regular basis. If there are major temperature
differences on the roller defects will occur. The two heated rollers should be
checked periodically to ensure that they are parallel with each other.

28 of 73

If pressure is applied by air at both ends of the rollers and narrow width
panels are laminated frequently, a bow may form on the rollers. If this
condition exists, pressure applied to the centre of the panel will be less than
that applied to the centre. In severe cases there is a possibility that poor
adhesion of the resist to the substrate will result.
Laminating Temperature
During lamination the resist must be heated above its glass transition
temperature to make it semi-liquid and hence be in a state to be pressed into
substrate defects by roller pressure. Although the glass transition temperature
is about 350C, the resist must be heated to a higher temperature to account
for cool air and the heat sink effect of the substrate. Heat must pass through
the polyester support film prior to heating the resist. It has been shown that
the roller temperature, measured by a contact temperature-measuring probe,
should be 105-110 0C to provide optimum flow characteristics of the resist. On
many laminators the hot rollers are heated by resistance elements in the core
of the roller. If the contact gel used to transmit the heat from these elements
(firstly to the steel core and the rubber coating) is not operative, the heating
will be much slower and the rollers may not return to the set point between
lamination of subsequent panels.
The temperature indicated on the read out on the laminator is via a contact
probe situated at one end of the roller. If this contact point is dirty or loose it
will lead to an incorrect read out temperature.
Pressure
The dry film resist is heated to about 1100 C so that it becomes semi-liquid
and will flow under the influence of pressure. The pressure that is applied to
the rollers is to ensure that the dry film resist is forced into the micro
roughness and surface defects that are present on the copper surface.
Unless the pressure is sufficient to enable this action to take place, the resist
will not have the necessary physical properties to withstand subsequent
processing.
If insufficient pressure is applied, poor conformance of the resist to the
substrate irregularities will result. Development, etching or electroplating
chemicals will penetrate under the resist resulting in rejects being produced. If
the applied pressure is too high, the resist will be forced into any holes that
require tenting and the tent strength will not be sufficient to withstand
subsequent processing.
Pressure must be sufficiently high to enable the resist to flow into the macro
roughness of the panel formed by the different thickness of glass fibres used
in the construction of the dielectric substrate. A normal pressure range of 3-5
bars is used depending on the type of laminator.

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Speed
The resist requires a finite time to flow into the irregularities of the substrate
under the influence of temperature and pressure. The actual speed of
lamination determines the time of applied pressure.
The lamination speed is adjusted to give optimum conformance and at the
same time the productivity that is required. Lamination speed is 1,0 to 3,0
metres per minute.
The overall lamination parameters are a balance of temperature, pressure,
speed and substrate thickness. Substrate thickness is important since this will
impact the amount of heat required to obtain the correct temperature on the
panel.
If the speed is too high then the resist will not have sufficient time to flow into
surface irregularities and hence poor conformance. If the speed is too low and
all other parameters are at optimum, the resist will flow into tented holes
causing tenting failures.
Hold Time After Lamination
After lamination the temperature of the laminated substrate must cool to room
temperature as quickly as possible.

The resist is made semi-liquid at the laminating stage and as such will
flow into surface irregularities. Once laminated the resist must be cooled
quickly to prevent continual flow into holes that require tenting. If the
resist continues to flow into the hole the resist thickness around the
periphery of the hole will thin and may not have sufficient mechanical
strength to withstand subsequent processing. A tent failure will result.

The resist must stabilise prior to subsequent processing. The photo

sensitisers and photo initiators move during the time that the resist is
exposed to ultraviolet light and continue to move for a period after the
light is switched off. The polymerisation of the resist will stop once the
molecules are at rest. The higher the temperature of the resist, the
further the molecules will travel. This is why the resist should be cooled
as quickly as possible.

The minimum hold time after lamination is the time taken for the resist to
cool to room temperature.

The maximum hold time after lamination is normally four days. However,
to hold the boards for an extended time the panels should be covered in
black opaque plastic. Yellow light does contain an element of visual light
that dry film resists are sensitive. In the worse case, polymerisation will
occur and prevent development of the resist.

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PHOTEC*
Dry Film Photoresists

Exposure
Equipment
Lamp Type
Illumination Intensity
Exposure Energy
Phototool Quality
Degree of Collimation
Vacuum Delay
Exposure Unit Temperature

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EXPOSURE
The exposure process is the polymerisation of the oligomers/monomers in the
resist chemistry. Polymerisation is accomplished by exposing the resist to a
known amount of ultra violet radiation.
The following sections detail eight critical areas that should be taken into
consideration to ensure successful exposure.
Equipment
There are several different types of exposure units used in the industry which
range from single-sided exposure manual printers to double-sided exposure
fully automated types. Different types of light reflectors are used with varying
efficiency of light transfer. The height of these reflectors above or below the
panel to be exposed will determine the light energy reaching the panel. This
will directly impact the rate of exposure. The quality of the reflectors will
determine the ENERGY DISTRIBUTION across the exposure frame.
Light will not be reflected evenly across the frame leading to resist exposure
difference across the imaged panel. On some older manual exposure units
the difference in light energy across the exposure frame can be as high as
40%. This does mean that we can have a difference of up to one step on a 21
Step tablet across the frame.
Lamp Type
PHOTEC photoresists have a peak spectral absorption of about 360
manometers. Therefore, the lamp used must have a peak spectral output at
the same wavelength. If there is a mismatch between output of the lamp and
the absorption characteristics of the resist there may be incorrect exposure,
even if the required number of millijoules is applied. In general, the type of
lamp used is a high pressure mercury lamp. To obtain the required
wavelength output the mercury is normally doped with small quantities of
iron.
Lamps should be changed regularly as the efficiency of the lamp changes
with age. Regulating the current that is applied to the lamp controls the light
output. In addition, spectral output may also change. It is common practice to
change the lamps after 1000 hours of use. A meter is normally incorporated
in the machine to record the time that the lamp is used.
Some lamps are cooled with a water jacket around the lamp. This cooling
does prevent heat build up within the exposure machine but it also reduces
the amount of energy transmitted. In severe cases this may increase the
length of exposure time to reach the desired number of millijoules.

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Illumination Intensity
A short, high illumination intensity is preferred to a longer, low intensity
illumination. The optical density of the resist changes during exposure. Since
the resists are of the surface polymerisable type, the surface layer of the
resist will consume energy, resulting in reduced energy passing to the lower
levels within the resist. Therefore, unless there is sufficient energy intensity,
most of the energy will be consumed as it passes through the resist and the
resist at the copper interface will not be exposed sufficiently.
During normal exposure we will see an exposure difference between the
resist on the surface and that at the base of the resist. The difference in
exposure can be two steps on a 21 Step Density tablet. Two steps are a
reduction of 50% of the light energy.
Exposure intensity is measured in milliwatts.
The actual time of exposure in seconds is millijoules.
milliwatts
Millijoules = milliwatts x time
Exposure Energy
Each resist requires a certain amount of energy to reach the optimum
exposure state. The amount of exposure will determine the actual chemical
properties of the resist. In all cases the technical data sheet of the resist
should be followed.
If the exposure energy is too low, then the resist will be attacked by both the
developing solution and the subsequent processing chemicals. The adhesion
of the resist can be affected leading to open circuits after innerlayer etching
and short circuits on electroplated circuits.
If the resist is exposed with too high an exposure energy, the image on the
phototool will not be transferred in a 1:1 ratio. This means that the exposed
traces will be wider than on the phototool.
Phototool Quality
Phototool quality is extremely important for high circuit density products.
Image density ( Dmax ) should be in excess of Dmax 3,5. Edge definition of the
opaque areas should be sharp and well defined. Diffused image edges can
lead to variation in track widths after development or incorrectly exposed
edges which may cause problems in the development, electroplating or
etching processes.
Background clarity of the clear areas of the phototools is essential to ensure
short exposure times. A high background density may increase exposure
times by up to 100%. If not corrected to compensate for high background
density, poor resolution and resist side wall profile may occur.

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The use of phototool emulsion protection systems extends the life of the
phototool. When setting exposure times the thickness of the protective coating
(normally 3-5 microns) must be considered to ensure accurate line width
reproduction. This thickness increases the off-contact distance from the resist
and thus makes the beam collimation of the exposure unit more important. If
the exposure unit has poor beam collimation, the use of a phototool protective
system will be dependent upon the permitted deviation from the normal 1:1
reproduction of the phototool.
Degree of Collimation
To obtain accurate phototool reproduction, the exposing energy (light) which
is hitting the panel at right angels to the resist is required. This light should be
evenly distributed across the exposure frame.
Collimated light is defined as light that is very close (90 degrees) to the panel
surface. Normally the angle of declination is about 0,5 degrees. It must be
noted that the higher the degree of collimation, the more dirt and scratches
will have on the phototool. These defects will be reproduced on the exposed
panel.
There are several factors that can influence the angle at which the light hits
the panel being exposed. The light emitted by the exposure lamp passes
through several different layers before it actually reaches the photoresist
These include the glass or polyester vacuum frame, phototool, phototool
protective layer and the polyester cover sheet on the resist. All of these layers
can give diffraction of the light.
Any air trapped between any of the layers will also cause light scatter. This air
gap can lead to off contact printing. The actual print out image will be
diffused and lead to rejects.
Vacuum Delay
A vacuum delay is necessary to allow time for all the air between the various
layers to be removed. We need the closest contact possible between the
phototool and the photo-resist, the vacuum delay allows the time for the air to
be removed and for the phototool to pull down onto the resist surface. A
typical vacuum delay is about 10 seconds but for high circuit density boards or
high-resolution boards then the vacuum delay is increased up to 30 seconds
in severe cases.

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Exposure Unit Temperature

Heat is a key factor during exposure. Polymerisation reactions started by ultra
violet light can be continued by heat energy and continue after the light
energy has been stopped. This may result in over exposure of the resist even
if the number of millijoules applied is correct. The actual degree of over
exposure caused by the heat in the exposure unit will depend on the actual
temperature and the inhibitors used in the formulation of the resist.
The exposure unit should have sufficient airflow within the unit to remove the
heat emitted by the lamp and to maintain the temperature within the unit at or
near room temperature.

35 of 73

PHOTEC*
Dry Film Photoresists

Development
pH concentration
Resist Loading
Temperature
Development Time (breakpoint)
Spray Nozzles
Antifoam
Filtration
Water Rinsing

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PHOTEC*
Dry Film Photoresists

Development

37 of 73

DEVELOPMENT
Development is the removal of unexposed portions of the negative working
resist. The development stage is critical as it determines the quality of the
resist remaining on the surface in terms of track profile, adhesion, etc.
As circuit density increases, the track width becomes smaller and more
closely packed. As such, the development process becomes more important.
On exposure the resist is polymerised and this alters the dissolution kinetics
between the exposed and unexposed resist.
The development mechanism is a diffusion controlled process, that is the
developing solution penetrates the unexposed resist and partially removes the
resist in the form of a colloid of binder polymer carboxylate salts. This layer
must then be removed by mass transfer of developing solution on the resist
surface and mechanical action by spray pressure before the next layer can be
attacked.
Eight key factors must be taken into consideration to achieve the correct
development action, cleanliness of the developed surface and optimum track
profile.

pH concentration of the developing solution

Resist loading within the developing solution

Temperature of the developing solution

Development Time (breakpoint): removal of the resist

Spray nozzles (type, volume of solution, spray impact)

Antifoam type and quantity

Filtration

Water rinsing (time and temperature)

The above factors demonstrate how the mechanical aspects of the

development machine and the chemical control of the process are extremely
important. Equipment design is very important and often the dry film resist
supplier has to use equipment that is already installed. However, the resist
supplier must ensure the following points so that resist performance is not
jeopardised.

The spray from the nozzles is effective and even over the entire board
surface. Development is even on the upper and lower board surfaces.

The spay impact pressure is sufficiently high to remove unexposed resist

from within fine lines and spaces and yet is not too high to break tents,
particularly those over oblong holes.

There is no puddling on the upper surfaces of the panel.

38 of 73

If more than one chamber is incorporated in the development part of the

machine, the space between the chambers should be clean and the
conveyor mechanism should remain wet. This can be achieved by using
misting nozzles.

Rinsing is an integral part of the development mechanism. Ideally, the

rinsing time should be 50 % of the development time.

Drying reduces swelling of the resist that occurs in the development stage.
If wet resist passes directly to a cupric chloride etching solution, increased
organic contamination may occur in the etchant.

The development mechanism is a diffusion controlled reaction, The sodium

carbonate reacts with the carboxylic (acid) radicals in the unexposed resist
and solubilises the resist. This carbonate resist mixture must be removed with
fresh sodium carbonate before the reaction may proceed.
Dry film resist is not dissolved in the developing solution, but is held in
suspension in a colloid form. Any mechanism by which this colloid is broken
down can lead to scum formation on the panel surface. It may also appear as
an oily substance on the solution surface. These mechanisms include
mechanical stress created by sheer forces in the pumps, spray nozzles, antifoams, dry film resist load in the development solution, etc.
If the colloid is destroyed then a scum will deposit in the developing solution
and an oily substance may be seen floating on the surface of the developing
solution.
COOH
COOH
COOH
Carboxylated Polymer

COONa
+ Na 2CO3

COONa
COONa
Sodium Salt
(Colloid)

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pH Concentration
The concentration of sodium carbonate used for development must be within
the range specified for each dry film resist. If the concentration is too low the
unexposed resist will not be completely removed and a scum remaining on
the surface will lead to etching or electroplating problems. If the concentration
is too high the resist will be attacked at the resist substrate interface leading to
poor track profile, and in severe cases, lifting of the resist. This in turn will lead
to electroplating deposits under the resist or track width reduction during
etching.
The dry film resist has acid radicals within its chemical structure. As the resist
reacts with the sodium carbonate, the acid radical is neutralised and the pH of
the developing solution will fall. If the pH of the developing solution falls below
a specified pH, the developing mechanism will cease. Therefore, it is essential
to replenish the developing solution by either pH control, conductivity, or area
of resists developed etc.
Resist Loading
The quantity of dry film resist within the developing solution is defined as
resist loading. As resist loading increases, the dissolution kinetics is changed
and therefore the speed of development changes. There is also a greater
tendency for the colloid resist particles to become unstable and precipitate
back onto the panel. This leads to open circuits in the case of pattern plating
and short circuits in the case of innerlayer production or circuits produced by
the tent and etch technique.
The specific recommendation for resist loading will depend on the type of
circuit being produced. Circuits with lines and spaces greater than 150
microns a loading of 0,4 square metres of 40 micron thick resist per litre of
developing solution is recommended. As the lines and spaces become
smaller, the resist loading becomes correspondingly lower. For lines and
spaces of 100 microns and lower, the resist loading should be less than 0,1
square metres per litre of developing solution. (See Appendix 1 for method of
analysis for resist loading in developing solutions.)
The dry film resist has acid radicals within the chemical structure. As the resist
is dissolved in the sodium carbonate solution this acid radical is neutralised
and the pH of the developing solution will fall. A 10-gpl Sodium Carbonate
solution will have a pH of about 11,2.

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Temperature
Most dry film resist specifications require that the temperature of the
developing solution be controlled within close limits. Normally this is the
optimum temperature plus or minus two degrees Celsius.
Thermostatically controlled heaters are required to control the temperature. If
the action of the pump mechanism generates heat the developing solution
temperature will rise and could exceed that set on the heater thermostat. In
this case cooling coils are also necessary to remove this excess heat. If
persistent problems arise always check the actual temperature of the solution
with a thermometer; never solely rely on the temperature indicated on the
development machine.
When the developing solution temperature is too high the speed of
development is greater and will lead to over development unless the total
development time is reduced. It will also give rise to a poor resist side wall
profile. A high temperature may lead to breakdown of the colloid and give rise
to scum on the panel surface. If the temperature of the developing solution is
too low then under development can occur and leave resist residues on the
panel surface and also give a larger foot to the resist profile.
Development Time (Breakpoint)
The minimum development time is the time taken for the resist to be removed
from the copper surface. Actual time in seconds will depend on a number of
factors including concentration and temperature of the developing solution,
volume of solution being sprayed onto the surface, type of nozzle, height of
the nozzle above the surface, etc.
For PHOTEC dry film photoresists, a breakpoint is required when the resist is
50-60% developed through the total effective spray length of the developing
machine. Note: The effective spray length may not be the overall length of
the developing machine. It is essential to inspect the machine and check the
actual length where the developing solution is sprayed onto the panel.
If the breakpoint is less than 50% of the total effective spray length over
development will occur. This in turn will lead to a poor resist sidewall profile
and undercut at the resist to copper interface. This results in under plating in
the case of pattern plating or over etching when innerlayers are produced or
the tent and etch technique is used.
If the breakpoint is greater than 60% then under development will occur.
Under development will lead to track width reduction in the case of pattern
plating and in severe cases will lead to plating inhibition or plating adhesion
failures.
In the case of etching innerlayers under development will lead to a track width
increase. In severe cases this may also lead to organic contamination in the
etching solution. Organic contamination in the etching solution will give small
areas of copper not etched on the surface (copper spots).

41 of 73

Spray Nozzles
Development is a diffusion-controlled mechanism. This means that the
developing solution must diffuse through the unexposed resist and through
the interaction of the sodium ion in the sodium carbonate solution react with
the carboxylic acid groups within the resist to form a colloidal particle. These
colloidal particles are then washed from the resist surface by fresh developing
solution. As the colloids are removed it leaves the surface in a condition for
more sodium carbonate to diffuse into the resist surface. This mechanism is
repeated until all the unexposed resist is removed.
Because resist removal is a diffusion controlled mechanism, a large volume of
low pressure sodium carbonate to reach the resist surface is required during
the first stage of development. To achieve, spray nozzles are used in the first
part of the development machine that spray a cone shaped pattern onto the
surface (i.e. cone nozzles). These cone nozzles give a low pressure on the
resist surface. It is recommended that each nozzle deliver in excess of 4 litres
per minute of developing solution. (A typical cone shaped nozzle will have a
spray impact of 0,4-0,5 Bar on the panel surface.)
To ensure the complete removal of resist at the base of fine lines and spaces
a higher pressure is required so that the developing solution will reach the
base of resist at the resist to copper interface. In fluid dynamic terms this is a
deep recess. A nozzle that delivers a fan shaped spray pattern is used for
this purpose.
The nozzle with a fan shaped spray is referred to as a high impact nozzle and
will have a typical spray impact of 8-9 Bar on the panel surface. Equipment
design is important to achieve the correct development of the resist across the
entire panel. Nozzle height and the angle of the nozzle jet must be such that
all the entire panel is sprayed at equal volume and pressure and that no
overlapping of the sprayed solution occurs. Any overlapping of the sprays will
reduce the effective pressure that impinges onto the surface. Prevention of
development solution puddling on the top of the panel must be prevented,
otherwise this will affect the replenishment of fresh solution on the resist
surface.
To even out the differences in solution replenishment on the top and lower
panel surfaces different spray pressures are used between top and bottom.
Normally a 0,2 - 0,3 Bar higher pressure on the top spray bar is used. Typical
spray pressures for development are Top 1,5 Bar and Lower 1,3 Bar.
However, the exact spray pressure is equipment related and should be
arrived at experimentally.

42 of 73
Antifoam
The type and quantity of any antifoam used in the development solution will
determine the stability of the colloid formed. If the incorrect antifoam is used
precipitation within the development solution will occur. This may lead to scum
formation on the panel surface that will interfere with the subsequent plating
or etching operations. To eliminate these problems, an antifoam that is a
polyethylene oxide or polypropylene oxide block copolymer based should be
used.
Siloxane based antifoams are known to cause instability of the colloids in the
development solution and give rise to scum or sludge. Silicone based
antifoams should not be used as they may provide problems in subsequent
processing operations such as electroplating. Trials should be made with all
new antifoams to check for colloid stability prior to use on production.
The concentration of antifoam used should be minimised to limit the foam
build-up in the development solution. Actual concentration used should be
within the range recommended by the supplier.
Filtration
To prevent the possibility of resists particles or large colloidal particles being
re-deposited back onto the panel it is essential to filter the solution. The filter
should be in line between the pump and the spray bar manifold and equipped
with filter to remove particles greater than 30 microns. The filters should be
changed regularly to prevent loss of developer solution volume being supplied
to the spray nozzles. Pressure indicators should be fitted into the spray
manifold after the filters; this will give a more accurate indication of the spray
pressure.
Water Rinsing
Water rinsing after development is an integral part of the process. The type,
volume and temperature of the water are important to ensure dry film resist
performance. Water with a hardness of 8 - 12 on the DIN scale should be
used. (See Appendix 4 for water hardness conversion.)
The reason for using slightly hard water for rinsing is that the divalent
cautions. Calcium and magnesium converts the soluble sodium form of the
polymers present on the resist sidewalls after development into less soluble
carboxylate salts. This effectively stops further development while improving
both resolution and resist sidewall profile.
Soft water or softened water is not an effective rinsing medium. The pH of soft
water is easily affected by drag-in of developer solution and in severe
circumstances may continue the development action.
The pH of the rinse water should be less than pH 9,0 and the temperature of
this rinse water should be less than 30 0C to stop development action and
prevent attack on the resist surface.

43 of 73

PHOTEC*
Dry Film Photoresists

Etching

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Photoresists are employed as an etch resist in the print and etch technology
for the production of innerlayers or in the "tent and etch" method of final circuit
production. The etchant used in these technologies is primarily cupric chloride
or ferric chloride. Following the etching process defects can remain on the
substrate in the form of copper spots or fine shorts.
This section details the chemistry involved with the etching process and some
of the reasons for defects. In addition, means of preventing these defects will
be provided. It is essential that care be taken to identify the cause of the
problem to enable the corrective action to be taken so that the problem may
be eliminated.
Factors Affecting Copper Etching

Substrate and Substrate Preparation

Dry film photoresist exposure and development
Cupric chloride etching solution

Substrate and Substrate Preparation

The innerlayer copper foil or the electroplated copper used in the tent and
etch process must be checked for the defects listed below.

Epoxy resin through pinholes in the copper foil during lamination of the
substrate
Copper nodules on the plated via hole boards or tent and etch panels
Excessive shiny spots on the surface
Heavy oxidation of the copper surface
Handling defects such as scratches, dents or fingerprints
Incomplete removal of any anti-tarnish coating

The standard practice of using 18 micron copper foil for innerlayers and the
increasing use of 9 micron copper has highlighted the problems with pores in
these thin copper foils.
Epoxy resin
During the substrate manufacture the epoxy resin of the dielectric flows
through pin holes forming circular spots of epoxide resin on the surface.
These epoxide resin spots are not removed during normal surface preparation
of the copper prior to resist application. These spots may change from circular
in appearance to an elongated form after any brushing operation. In general
resin spots should not exceed one spot per square metre.
Corrective Action: Incoming inspection should be able to detect this problem
without difficulty.

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Copper Nodules
The increasing requirement for buried via holes and panel plated copper for
tent and etch technology has necessitated drilling and metallisation (often
direct metallisation) followed by electrolytic copper plating. This three step
sequence may result in both nodules and gas pits on the surface prior to
lamination. Copper nodules may result in copper remaining on the etched
surface. Both copper nodules and gas pits may result in poor conformance of
the resist at the lamination stage and allow the development or etching
chemistry to penetrate beneath the resist and lead to open circuits.
Corrective Action: Inspect the panels after electroplating prior to imaging. The
most probable causes of nodules after electroplating include:

Thick electroless deposits in localised areas are caused by insufficient

control of the pre-activation and activation stages prior to electroless
copper deposition. These nodules appear after electroless copper and
produce localised high current density areas in the electrolytic copper
stage producing higher than average copper deposit thickness.

Particulate material in the electrolytic copper electrolyte is co-deposited

with the copper. These particles may arise from edges of the panels
particularly if an excessive desmear operation has been carried out on
an in-line processing sequence.

Gas pits may be caused by insufficient control of the additive system in the
electrolytic copper electrolyte. Localised over concentration of these additives
may result in passivation which reduces the cathode efficiency of the
deposition process and result in hydrogen evolution and a localised reduction
in copper thickness.
Excessive "Shiny" Spots
The excessive shiny spots on the copper foil, as received from the laminate
supplier, are generally caused by the glass cloth used for the construction of
the dielectric. A high localised thickness where the weft and the warp of the
glass fibres cross may lead to shiny spots (depending on the diameter of the
glass fibre used in the construction) being formed after pressing the copper
foil onto the dielectric. The excessive pressure on these high spots during the
pressing operation to produce the laminate changes the structure and
hardness of the copper in these localised areas. Any differential hardness or
structural differences in the copper cause changes in etch rates, often slowing
the etch rate such that reduced copper thickness spots are left on the surface
after etching.

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Corrective Action

After laminate preparation, check to see if pumice, pumice brush,

abrasive brush or chemical pretreatment have removed these spots.

Check sprays or brush pressure. Increase pressure if necessary.

Ensure that the pumice concentration is correct; increase pumice

concentration to 20 volume percent.

Ensure pumice suspension is acidic in nature.

Change pumice more frequently.

Check pumice grade being used.

If equipment is suitable, consider use of aluminium oxide as

replacement of pumice.

If chemical pretreatment is used, increase the thickness of copper

etched to 1,0 micron.

Heavy surface oxidation

Heavy surface oxidation should be confined to those panels that have been
wet processed prior to resist lamination. If the copper oxide is not removed it
may cause a "lock in" of some resists.
Corrective Action

Check to ensure that the rinse water after electro-plating is clean and
that the panels are rinsed sufficiently.

Increase the temperature and airflow volume during the drying

operation.

Ensure that any through holes are dry before stacking the panels

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Anti-tarnish
The anti-tarnish coating on base laminate as received from the laminate
supplier is normally of the chromate type. Excessive chromate conversion
coating may not be removed during cleaning and could either lead to a "lock
in" of some resists or may etch slower than surrounding copper.
Chromate layers are normally removed using an acidic medium. Alkaline
pumice spray or pumice brush operations may lead to incomplete removal of
the chromate layer.
Corrective Action

Ensure that the pumice suspension is acidic in nature.

Change pumice more frequently as a build-up of chromate may occur
in the pumice suspension. If electrolytic methods are used to remove
the chromate layer, ensure that the correct anodic voltage is applied for
the correct time

Dry Film Photoresist Exposure and Development

It is not generally recognised that the combination of exposure and
development may provide problems during the etching operation.
As part of the resist matrix, a dry film resist comprises oligomers, sensitisers
and photoinitiators that during exposure to ultra violet radiation combine
together to form polymers and stable reaction bi-products. Insufficient
exposure will lead to an excessive quantity of these chemicals remaining on
and in the resist matrix. These unused chemicals react in the acidic media of
the etchant to produce an oily product which, if not removed, will float on the
surface of the etchant.
Underdevelopment of the resist leaves a scum residue on the copper surfaces
that will not be completely removed by rinsing and will prevent etching of the
copper surfaces. Underdevelopment also leaves a larger than normal "foot" at
the base of the resist track profile. This "foot" will be undercut during etching
and fall into the etchant. This again may lead to organic contamination in the
etchant.
Over development provides an unstable sidewall to the resist that is attacked
by the cupric chloride etchant. This will leach out photoinitiators, oligomers
and imaging agents from the resist, which unless removed by carbon
treatment, will provide an oily residue in the etchant.
It is recommended that the dry film resist content of the developing solution is
maintained below 0,2 m2 / litre. If the resist content is higher there is a danger
that the resist is re-deposited in a particulate form which is very adherent to
the copper surfaces and difficult to remove by water rinsing and prevents
etching. Any solid particulate material, especially sodium carbonate, will
penetrate into the unexposed resist and prevent development of the
underlying resist.

48 of 73
Rinsing is an integral part of development. Rinse stations should be at least
50% of the development stations.
Development should be maintained at 1,3 - 1,7 times that of the time for
minimum development breakpoint.
Corrective Action

Check that the lamination temperature is not too high and that the hot
rollers have a good thermal profile. Hot spots on the hot roller may lead
to heat polymerisation of some resists. Panels should be cooled as
quickly as possible to room temperature and not stacked until this
cooling process has taken place.

Check for correct exposure level. In the case of PHOTEC resists,

ensure that the Step Tablet exposure is maintained between Step 7-9.

Ensure that the phototools are of good quality with no scratches or

pinholes in the opaque areas. The phototool should have opaque areas
of sufficient density to prevent partial exposure of the resist in areas
that should not be exposed. Scratches or "touch-up" marks in the clear
areas of the phototool will lead to partially polymerised resist that may
be removed during development and re-deposit back on to the panel at
a later stage of development.

The acuity (the change between the clear areas and the opaque areas
of the phototool) should be a sharp boundary. If there is a gradual
change between clear and opaque areas this will lead to partial
exposure along the edges of these tracks and development problems.
In severe cases this may increase organic levels in the etchant.

Check for correct developer concentration. Follow the resist

manufacturer recommendations for concentration and developer
solution temperature.

Ensure that there is no particulate matter in the development solution

by using a filter of 10-30 micron filter size

Check for the resist loading in the developing solution. (See Appendix
1 for the analytical method.)

Ensure that the breakpoint of the development is correct in order to

obtain a stable sidewall of the resist

Rinse water temperature should be between 12-27 0C and rinse water

time should be at least 50% of the development time

If necessary, increase the hardness of the rinse water to 8 - 12 dH.

Reduce scum formation by using water containing less than 10

mgm/litre of divalent cautions for make up and replenishment.

49 of 73

Reduce the amount of antifoam and ensure that it is a compatible type

with the resist being developed. The higher the concentration of
antifoam, the higher the formation of scum and the chance of residues
remaining on the panel after development.

Clean all transport rollers to prevent any particulate matter pressing

into the undeveloped resist.

Ensure that all spray nozzles in the development section are not
blocked or worn. Worn, blocked or partially blocked nozzles may cause
poor or underdevelopment.

Ensure that as the polyester foil is removed no flakes of this material

are formed that will be attracted to the resist surface by electrostatic
electricity.

Check the resist after development and drying to see if the resist is
correctly developed and rinsed. Over development or rinsing with too
soft water can leave a soft resist that can be attacked by the etchant.
After development and drying, place the panel in a tank of water for
one minute. Take out the panel and hold it vertically. The water should
immediately run from the resist (i.e., it should immediately de- wet).
The resist should have a gloss appearance without any matte areas

Ensure that the resist is thoroughly dried after development and

rinsing. The resist swells slightly during development and will shrink as
soon as it comes in contact with an acidic medium. Heating the resist
at this stage stabilises the sidewall and shrinks back the resist to its
correct size and prevents leaching into the etching solution.

50 of 73
ETCHING
The primary etchant that is used to produce innerlayers and boards by the
tent and etch process is a non-proprietary solution of cupric chloride. This
etching solution contains cupric chloride and hydrochloric acid. The etch rate
and the etch factor is determined by the concentrations of these two
chemicals in solution.
The basic chemistry of the etching mechanism is:
CuCl2 + Cu0

Cu2Cl2

Cu2Cl2 + 4 HCl

2CuCl32- + 4H+

During this reaction there is a build-up of the insoluble Cu2Cl2 (cuprous

chloride). Insoluble Cu2Cl2 precipitates onto the surfaces preventing etching at
these points. Further reactions take place with the oxidant to oxidise the
cuprous to cupric chloride.
With hydrogen peroxide each gram of copper etched requires 75 ml of 100
volume hydrogen peroxide and 1 ml of 35% hydrochloric acid.
Cu2Cl2 + 2HCl + H2 O2

2 CuCl2 + H2 O

2 CuCl32- + Cl2

2CuCl2 + 4 Cl-

With chlorine:

It is normal for these reactions to be controlled by the use of an OxidationReduction Potential control system (ORP). However, the oxidant added to
control the copper chloride etching solution is not only consumed by oxidising
the copper from the cuprous to the cupric state.
Organic material dissolved from the dry film resist is also oxidised and the
total reaction consumes a higher amount of oxidant. It has been shown by xray mass analysis that the oily residues present on the surface of the cupric
chloride etchant is a mixture of oligomers, photoinitiators and imaging agent. It
has been determined that the oxidising agent in the etchant affects all
aqueous developable photoresists. It has also been determined by
experiment that it is essential to control the Oxidation Reduction Potential
closely as the range of eliminating or obtaining copper spots on an etched
panel is within a range of 20mV.

51 of 73
Control of Etching Solution

Maintain the oxidation-reduction potential at 540 +/- 40 mV. Below

500mV the incidence of copper spots increases considerably.

Continuously carbon treat the cupric chloride etchant to remove

organic material.

Remove any sludge formed on the surface of the etching solution at

least once per week.

Clean once per week the conveyor and squeegee rollers, especially
rollers at the entrance of the etching machine.

The "oily" layer on the surface of the etching solution may be reduced
by heating the developed boards to a temperature of 40-60 0C prior to
etching.

The oil-adsorbing mat (polypropylene-type) in the etching machine

should be maintained regularly.

If pumped through the spray nozzles, the oily layer forms an emulsion
that is strongly adherent to copper surfaces.

Increase the addition rate of the oxidant (hydrogen peroxide or chlorine

gas) for organic material.

Ensure that the filters on the etching machine are maintained regularly.
Filters capable of removing 10-30 micron particles are recommended.

Ensure that the total etch time is at least 1,3 times the minimum
etching time.

Cuprous chloride concentration increases as the oxidation reduction

potential decreases. At 540 mV the concentration is about 1 gm /l and
at 450 mV it rises to about 20 gm /l.

52 of 73

PHOTEC*
Dry Film Photoresists

Resist Stripping

53 of 73

RESIST STRIPPING
The objective of resist stripping is to remove the resist from the copper panel
(including fine lines and spaces), while ensuring a non-oxidised surface.
Most alkaline type dry film resists do not dissolve in the stripping solution but
are detached from the copper surface in small flakes. This extends the
working life of the stripping solution.
Stripping solutions are normally alkaline metal hydroxides, such as sodium or
potassium hydroxide, or based on amines such as mono or tri ethanolamine
and tetra methyl ammonium hydroxide.
The stripping solution should break the polymer chain at the cross-linking
point of the three dimensional structure, which is formed during the
polymerisation of the resist and before the bond between the resist and the
copper surface is broken. The stripping mechanism depends not only on the
cross-link density of the resist but also the number of carboxylic acid groups
on the polymer chain. Therefore, the type and concentration of stripping
solution should be optimised for each resist and these must be set to allow
the stripping solution to have time to penetrate the resist and break the
polymer chain before the resist-to-copper bond is broken.
If stripping trials are conducted in the laboratory prior to production it must be
noted that the resist characteristics do change during the electrolytic
deposition of copper and tin-lead or tin. This means that any stripping trials
should be conducted on panels that have been through the deposition cycle
used on production.
The trials are performed not only to optimise the stripping time and flake size,
but also to set the concentration of stripping solution that minimises the
swelling of the resist in the solution. To obtain complete stripping of the resist
from within fine lines and spaces the resist must be removed before it swells
and is trapped by mechanical forces within these fine traces.
The stripped flake size for any resist depends on four major factors:

The type of stripping solution

The concentration of the stripping solution
The temperature of the stripping solution
Design of the stripping equipment

When using any stripping solution the stripping time and stripped flake size is
a balance of concentration and temperature. The higher the concentration
results in a faster stripping time but with a larger flake size. Conversely, a
lower concentration will give smaller flake size but the stripping time is much
longer. Increasing the temperature will reduce both the stripped flake size and
the stripping time.

54 of 73
Stripping is a diffusion-controlled mechanism. A high volume and spray
pressure through each spray nozzle is required. Typically, a minimum flow of
4 litres per minute at a pressure in excess of 1,5 Bar is recommended. When
alkaline metal hydroxide solutions are used for stripping electroplated boards,
a pressure as high as 6-10 Bar is often used.
An ideal equipment configuration is for the spray jets in each stripping module
to be angled at 30 degrees in the four axes of the board. This will ensure that
the resist is stripped between fine tracks. Where there is a possibility of
overhang of plated metals onto the resist surface, particularly in high current
density areas, it is beneficial to have a flooded stripping cell as the final
stripping section. With PHOTEC resists it is helpful if the plating overhang is
less than 7-8 microns onto the surface of the resist.
Antifoam may be necessary to prevent foaming of the solution. Any antifoam
used must be in a minimum concentration and compatible with the stripping
solution being used. The antifoam used in the development solution will
probably not be suitable for the stripping solution. The total alkalinity of the
stripping solution determines which type of antifoam is suitable.
To prevent the dry film from being dissolved in the stripping solution, it is
necessary to filter the solution to remove the stripped flake of resist. This
filtration will extend the working lifetime of the stripping solution. There are
many different types of filtration methods, including external or internal belt
filters or angled screen types. PHOTEC resists have been demonstrated to
work with all of these. If an angled screen is used as the filtration method, the
actual angle of this mesh may have to be adjusted to obtain the best results.
For optimum stripping it is necessary to replenish the stripping solution. This
may be achieved by either analytical or by bleed and feed methods. In all
cases, the area of PHOTEC resist stripped should not exceed 0,5 square
metres per litre of stripping solution. The following example demonstrates the
effect of stripping solution concentration on stripping time and stripped flake
size.
Dry film resists thickness: 50 micron
Stripping solution: Sodium Hydroxide
Temperature: 550C
Agitation: Zero

Concentration (%)
0,5
1,0
1,5
2,0
2,5

Complete removal of resist

Time (sec.)
360
150
100
70
60

*Self releasing from copper

Stripped
Flake Size
~2 x 10 mm*
~10 x 20 mm*
Large sheet**
Large sheet**
Large sheet**

**Requires agitation to release from copper

55 of 73

PHOTEC*
Dry Film Photoresists

Questions and Answers

56 of 73

COMMONLY ASKED QUESTIONS

Where is PHOTEC manufactured? Where is it slit?
PHOTEC is currently manufactured in Japan and Malaysia. It is produced
with Japanese products and slit on machines that are specified and run by
Hitachi Chemical engineers.
Enthone-OMI has been the exclusive distributor and marketer of PHOTEC
dry film resists throughout Europe. Backed by unmatched technical
support, PHOTEC dry film rolls are custom slit at Enthones ISO 14001
certified facility in The Netherlands.
How is consistent quality and supply assured?
All manufacturing is carried out under the same exacting conditions. The
products used during manufacture are identical and quality control is the
same.
There is always 6-8 weeks of Jumbo rolls in stock at Enthone Benelux.
This stock is based on our forecast for sales over a period of 5-6 weeks
and the delivery time from the manufacturing site.
What is a Jumbo Roll?
A jumbo roll is a master roll that is produced during manufacture. This roll
is typically 1,5 - 1,6 metres wide and with a length of up to 2 kilometres.
How do we know which type of PHOTEC to stock?
The type of PHOTEC inventoried is based on customer current and
forecasted buying patterns.
What cutting widths are available?
Enthone slitting facility is capable of cutting widths according to customer
requirements within the range 145mm to 610mm with an accuracy of +/1mm.
What are the standard core sizes?
The core size relates to the internal diameter of the core. 3 inch and 5 inch
core sizes are available.
What is meant by a 6-inch core size?
The 6-inch core was originally quoted when large diameter paper cores
were first introduced. It was a standard core for electrical coils that utilised
the outside diameter of the roll. The paper cores had a wall thickness of
0,5 inches; the inner diameter was the normal 5-inch.

57 of 73
What class of clean room is recommended?
Class 10,000 clean room is required for todays PWB lines and spaces
(i.e. 75 micron). The air quality should be checked regularly and all clean
room procedures must observed.
How should rolls be stored?
To prevent deterioration of the dry film resist, reduction in photosensitivity,
edge fusion, etc. the rolls should be stored between 5 - 20 OC with a
relative humidity of 40 - 60 %.
If the temperature is lower than 5 0C water may condense on the rolls
leading to softening of the resist and the potential for the defects,
including:

Increased adhesion of the film at the lamination stage resulting in

resist lock-in, as well as plating or stripping problems.

Thinning of the resist (especially around holes) leading to tent

failures and other defects.

If the temperature is higher than 200C for any length of time edge fusion
and deterioration of the photosensitive properties may result.
Note: When the temperature is reduced, the relative humidity in the air will
INCREASE.
What is the thickness of the polyethylene and polyester (Mylar) films?
The polyethylene has a thickness of 25 microns.
The polyester thickness for the standard resists is 20 microns.
What is the optimum cleaning cycle prior to lamination?
The optimum cleaning cycle imparts the correct surface topography and
cleanliness to achieve the best resist adhesion values. This may be
achieved by chemical or a combination of chemicals and abrasive
techniques.
What is the maximum unevenness of the copper surface?
PHOTEC resists have good conformance properties. However, for 40 or
50 micron thick resists, the macro roughness of the glass weave within the
substrate should not exceed 9 microns.

58 of 73
What conformance (conformability) may be achieved with PHOTEC
resists?
PHOTEC dry film resists provides excellent conformance properties
versus competitive resists. When laminated properly, PHOTEC resists will
conform to substrate defects of up to 9 microns when using a 40-micron
thick resist. In the case of a scratch defect, the width of the scratch should
be less than 100 microns.
Note: A resist is a viscous liquid when laminated. Fluid dynamics will not
allow it to flow into deep narrow cuts.
What surface roughness is recommended for optimum adhesion of the
resist to the substrate?
The main purpose of a micro-roughened surface is to provide key locking
points for mechanical adhesion of the resist. Surface roughness
recommendations include:
Ra
0,2 0,4 microns
Rmax
2,5 3,0 microns
Ra is the average distance of the roughness profile from the centre line of
the surface.
Rmax is the deepest individual roughness depth over the total measured
length.
To ensure sufficient anchor points for the resist, a minimum of 25 peaks
per 100 microns is recommended.
What is the resist adhesion mechanism to the copper substrate?
Immediately after lamination the adhesion mechanism is purely
mechanical. After a period of ~5 minutes a chemical bond forms between
the resist and the copper substrate. This chemical bond is a key factor in
determining the resistance to under plating or undercut during etching.
Is there any adhesion promoters in the PHOTEC chemical constituents?
Unlike other resists, PHOTEC does not contain any sulphur-containing
compounds within the chemical formulation. PHOTEC does contain a
small amount of nitrogen, which is in the imaging agent formulation.
How does PHOTEC achieve good adhesion values?
The main adhesion forces are achieved by the covalent chemical bond
formed between the hydrogen atom in the acrylate molecule and the
copper substrate.

59 of 73
How long may panels be held between lamination exposure
development?
Typically, panels may be held 3-4 days between lamination and exposure.
However PHOTEC may be held up to 7 days if they are covered with non
transparent black polyethylene and kept stored at a temperature of less
than 20 0C and a relative humidity of 40-60%.
Between exposure and development ideally they should be developed
within 24 hours but can be held up to 3 4 days if kept covered with black
polyethylene and stored in controlled conditions.
NOTE
PHOTEC in common with all dry film photoresists are unable to be
developed if exposed to a light intensity of 3 5 mJ/cm2. The yellow lights
used in the process areas do have an element of light in the visible light
wavelength and all dry films are sensitive to visible light.
What happens if panels are stored longer than recommended or outside
the recommended storage conditions?
Lock-in of the resist to the substrate and incomplete development may
occur leading to plating or etching defects.
What wavelength of light is most suitable to expose PHOTEC resists?
PHOTEC has a peak spectral absorption at 360 nanometres. Each type of
PHOTEC has a slightly different spectral response.
Checks of light output using a radiometer are not entirely accurate since
each radiometer is calibrated for a slightly different light wavelength. To
control exposure it is ideal to set the exposure level using a graduated
grey scale.
What is the relationship between exposure energy and time of
exposure?
Exposure Energy (E) = Light Intensity (I) x Time (T)
E=IxT
mJ/cm2 = mW/ cm2 x t
What happens to the exposure time when the exposure lamps get older?
As the lamps age with use, two effects can be observed.

The lamp experiences a reduction in power. The electrical current

setting on the lamp must be increased to maintain the same light
output. Unless this is carried out, the exposure time becomes longer.
Frequent checks must be made to ensure that the exposure energy
applied to the resist is constant.

60 of 73

There is a shift in the peak spectral output from the lamp. This means
that there is a spectral mismatch between the peak spectral
absorbance of the resist and the peak spectral output of the lamp.
Once again, a longer exposure time or a reduction in the quality of the
side wall profile of the resist is observed. This results in lower
productivity or reduction in quality.

What is the minimum hold time between exposure and development?

The resist is exposed by free radical polymerisation and the molecules in
the resist are disturbed by the action of the ultra violet light radiation.
Unless the exposure machine is well ventilated to remove the heat emitted
by the lamps (not all the electrical energy supplied to the lamp is emitted
as light), a part of the energy is transformed into heat. This heat will again
disturb the molecules within the resist.
The time between exposure and development must allow for the
molecules in the resist to normalise. The photoinitiators may still migrate
when the resist is above room temperature and for a short period of time
after the exposure energy is switched off.
Time between the exposure and development is the time taken for the
resist to reach room temperature. If development is conducted before the
resist attains room temperature, the side wall profile of the resist will not be
optimum.
What happens if the polyester support film is removed too long after
exposure and before development?
If the polyester is removed prior to or during exposure the oxygen in the
atmosphere may react with free radicals and form non-reactive products.
The polymerisation of the resist is accomplished by free radicals and if
they are converted to a non-reactive form the polymerisation will be
stopped.
What is the minimum exposure level that will prevent development of the
resist?
Most dry film resists only require an exposure level of 3-5 mJ/cm2 to
prevent development. This amount of energy can arise on the resist if the
resist is held too long under yellow light conditions within the exposure
room. Yellow lights have a small element of white light within the output
spectrum that many resists, including PHOTEC resists, are sensitive.
What is the adhesion value of the polyester support foil to the resist?
A nominal value for all types of PHOTEC resists is 20 grams per two
centimetre wide strip.

61 of 73
Is a clean room required for lamination and exposure?
The objective of lamination and exposure is to reproduce a reliable image
on the copper surface that is on the phototool. Dirt and dust will cause a
problem in giving either short or open circuits. For normal 125 micron lines
and spaces, an air conditioned room of Class 10,000 is suitable. As the
lines and spaces become closer together, the standard of the clean room
must improve. For 50 or 75 micron lines and spaces, the clean room
should be Class 1000.
Will I get the same exposure energy on the resist surface as shown on
the top of the exposure frame?
No. There are interposed films between the light source and the dry film
resist surface.

Glass or polyester exposure frame covers sheet

Phototool
Phototool protective coating
Polyester cover sheet of the resist

All of these films reduce the light passing through. In some cases the
actual amount of light reaching the resist surface is only 50% of that
measured on top of the exposure frame.

How do you determine the actual light loss and obtain the correct
exposure?
With a glass exposure frame it is not possible to place a U.V radiometer
between the two glass plates.
By placing the radiometer on top of the exposure frame, check the
relationship between the applied number of milijoules per square
centimetre and the step obtained on the graduated grey scale. Once this
has been established, set the number of milijoules applied by measuring
the milijoules every working shift.
How should the phototool and the exposure frame be cleaned?
Dependent on the class of circuit being produced the number of cycles
between cleaning is variable.
Generally, for lines and spaces of 150 microns and above the phototool is
cleaned with either solvent or sticky roller after every 25 exposures. For
lines and spaces of <150 microns it is good practice to clean after every 5
or 10 exposures. After each cleaning the phototool should be inspected
with a magnifying glass, to check for fibre or particulate matter.
It is good working practice to install an ionization blower above each print
machine.

62 of 73
How often should the phototool be changed?
It is good practice to use new phototools for each batch of circuits.
However, it is normal to change the phototool after every 250 exposures.
The action of placing the substrate on the phototool will lead to scratches if
it not covered with a protective coating.
You should also change the phototool if the light intensity passing though
the tool drops by a value of 10% versus the light intensity on a new tool.
What is a latent print out image?
The latent print out image is the formation of an image of the phototool
onto the PHOTEC surface. A print out image is formed by a change in the
structure of the imaging agent incorporated within the resist.
In the case of PHOTEC resists, the image is photochromic. This means
that on exposure to light the resist changes to a darker colour. The actual
colour change depends on the type of imaging agent and the degree of
exposure. A higher level of exposure will give more contrast between the
exposed and unexposed resist.
What is the optimum exposure level for PHOTEC?
Refer to the technical data sheet for the type of PHOTEC resist being
used. In general, it is normal to expose the resist to a grey scale of
between Step 7 and 9. After development, the step is determined when
the PHOTEC resists appears on the panel.
What is the Minimum Development Time (MDT)?
The minimum development time is the time taken to remove the
unexposed resist on the copper surface. The minimum development time
is also called the "breakpoint or wash off point. This time is reported
as a percent of the usable development machine or a percent of the
number of spray bars in the machine.
The Total Development Time is the minimum development time multiplied
by a factor of 1,3 to 1,7.
Total Development Time = Minimum Development Time x 1,3 to 1,7.
Is there an easy way to check the break point prior to lamination?

Using a water-soluble marking pen, draw several lines on the cleaned

panel in the direction that the panel will be developed. Laminate over
these markings.
During development, observe at which point the marked lines are removed
from the panel. The actual resist will be removed one spray bar before the
markings are removed.

63 of 73
What is the shape and size of the foot on the PHOTEC resist profile?
At the interface of the resist to the copper surface the resist will protrude
onto the copper surface. This protrusion is what is known as the foot.
The foot should not be greater than 2-3 microns long.
Is there an easy way to determine if post development rinsing is
satisfactory?
After the panel has been developed, rinsed and dried, take the panel and
immerse it in the rinse water for one minute. Remove the panel and drain
vertically. If the panel completely de-wets the rinsing is effective. If the
panel remains wet, development residues are present and rinsing has
been ineffective.
Another way to determine satisfactory rinsing is to check the hardness of
the resist with a fingernail. After soaking the dried panel in the rinse water
for one minute, scrape the surface with the fingernail. If the resist
scratches or is removed slightly it is possible that rinsing is not effective
and the rinse water should be changed.
Why is drying necessary after post development rinsing and prior to
cupric chloride etching?
During post development rinsing, the resist swells slightly. Drying shrinks
the resist back to a normal state and reduces the organic contamination in
the etching solution.

64 of 73

PHOTEC*
Dry Film Photoresists

Appendices

Appendix

Title

Analytical method to determine the concentration

of dry film resist in developing solutions

Exposure

Asian/European Specification

Water Hardness

Hitachi/Strouffer/Riston Step Tablet

Line width variation between artwork and

final etched panel

65 of 73
APPENDIX 1

Analytical Method to Determine the Concentration of Dry Film

Resists in Developing Solutions
General
An aqueous dry film resist contains within its chemical structure a number of
carboxylic acid groups (R COOH). The number of these groups is specific
for each type of resist. In a development solution these carboxylic acid groups
have reacted with the alkali metal carbonate (Na 2CO3 or K2CO3) to form a
carboxylate group [i.e. R COONa)].
The analytical method used determines the alkali metal carbonate
concentration and continues further to determine the dry film resist
concentration.
Three reactions must be taken into consideration:
Na2CO3 + HCl

NaHCO3 + NaCl

NaHCO3 + HCl

NaCl + H2O +CO2

R COONa + HCl

NaCl + R COOH

Method
1. Mix the developing solution thoroughly.
2. With a safety pipette take a 5ml sample of the developing solution and
place in an Erlenmeyer flask.
3. Add 30 ml of deionised / demineralised water.
4. Add a few drops of 1% phenolphthalein indicator solution to the
Erlenmeyer flask. ( Colour of the solution will change to a red violet )
5. Using a magnetic stirrer and rotator agitate the solution evenly.
6. Titrate the solution with a 0,1 N Hydrochloric acid solution slowly until the
colour of the solution changes from red violet to the colour of the original
solution.
7. Note the volume of 0,1N Hydrochloric acid used = A ml
8. Continue with the same solution.
9. Add a few drops of 1% Methyl Orange indicator solution. The colour of the
solution will change to an orange colour. (continued on next page)

66 of 73
10. Titrate slowly with 0,1N Hydrochloric acid until the colour changes to pink.
11. Note the volume of 0,1N Hydrochloric acid used. = B ml
Note: The first titration determines the concentration of Sodium Carbonate
= A ml 0,1N Hydrochloric acid
Na2CO3 + HCl

NaHCO3 + HCl

The second titration determines the Sodium Bicarbonate concentration plus

the Carboxylate concentration
= B ml. 0,1N Hydrochloric acid
NaHCO3 + HCl
R- COONa + HCl

NaCl + H2O + CO2

R- COONa = NaCl

= A ml 0,1 N HCL
= B ml 0,1 N HCl

Calculations
Mls 0,1 N HCl for volume A is equivalent to mls 0,1 N HCl for volume A
Therefore we can calculate the mls 0,1N HCl equivalent to the carboxylate
Concentration B
B = B A
1.

Na 2CO3 %

2.

Dry film resist

concentration

0,1 x 106 x Aml x100

Sample volume 5ml x 1000
= Film calculation factor x 0,1 x B ml
5

Note:
0,1

0,1 N HCl If a different Normality is used a conversion

factor must be applied

106 =

Molecular weight of Na 2CO3 . If Potassium Carbonate is

used for developing then the factor 138,2 is used
(138,2 are Molecular weight of Potassium Carbonate)

FILM CALCULATION FACTOR : 7,25 (mean value)

67 of 73

APPENDIX 2

EXPOSURE
To calculate the correct exposure time from a known exposure time and the
resulting step obtained the following equation or table may be used.
This calculation only applies to a 21 Step Density Tablet with a density range
of 0,05 3,05 and a D = 0,15.
Exposure time for the desired step (T):
(Desired Step Reference Step)
= Reference time (TR) 2
(S)
(SR )

= TR

Step Obtained by Exposure

1
2
3
4
5
6
7
8
9
10
11
12
13
14

( S SR)

Multiple to Obtain Step 8

1,113
8,00
5,66
4,00
2,83
2,00
1,41
1,00
0,71
0,50
0,35
0,25
0,18
0,13

Example:
To find the correct exposure time when Step 5 is obtained in X seconds to
reach a desired Step 8.
Multiply X by 2,83

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APPENDIX 3

Asian/European Specification
Based on customer requirements both in Asia and in Europe, the following
surface specification is applied for production of 100-micron lines and spaces.
(The specification applies to each surface of a 500 mm x 500-mm panel.)
Item

Specification

Macro roughness
(glass weave roughness)

< 4 micron

Nodules

Zero

Scratches

< 1 ( depth < 5 micron)

( length < 100 micron)

Pin Holes

< 1 < 50 micron Diameter

0>50 micron Diameter

Indentations

all indentations must be < 4 microns

Deep
Diameter ( mm )
< 0,25
0,25 0,5
0,5 0,75
0,75 1,00
> 1,00

Number
No Spec.
< 50
< 25
<4
0

Panel Edge

Smooth.

Periphery of tented hole

No burrs or dishdowns

Surface roughness

R max
2,5 3,0 microns
Ra
0,24 0,4 microns
Peaks and valleys
20 26 per 100 microns

Moisture in through hole

None

Water stains

None

Water Break test

Water should remain on the surface

for minimum 30 seconds

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APPENDIX 4

Water Hardness
Water hardness is measured in milligram equivalent per litre of calcium or
magnesium ions.
1 milligram equivalent is equal to

20,04 mg/l Calcium ion

12,16 mg/l Magnesium ion

1 degree on the DIN scale is equal to 0,357-milligram equivalent per litre.

This is equal to 7,15 mg/l Calcium ion
4,34 mg/l Magnesium ion
1 degree on the DIN scale is equivalent to:
1,786 degrees French Hardness
1,237 degrees English Hardness
If the water hardness of the immediate rinse after development is too low, a
calculated addition of a 200 gm per litre solution of anhydrous magnesium
sulphate is added.
An addition of 1,075 ml for every 10 litres of rinse water will raise the
hardness by 1 degree DIN.

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APPENDIX 5

Hitachi/Stouffer/Riston Step Tablet

Hitachi
Stouffer
Step

41 tablet
41 tablet
Density

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41

0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
1.00
1.05
1.10
1.15
1.20
1.25
1.30
1.35
1.40
1.45
1.50
1.55
1.60
1.65
1.70
1.75
1.80
1.85
1.90
1.95
2.00

Hitachi
Stouffer
Step

21 tablet
21 tablet
Density

0.05

0.20

0.35

0.50

0.65

0.80

0.95

1.10

1.25

10

1.40

11

1.55

12

1.70

13

1.85

14
15
16
17
18
19
20
21

2.00
2.15
2.30
2.45
2.60
2.75
2.90
3.05

Riston
Riston
Step

17
25

Tablet
Tablet
Density

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25

0.05
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
1.00
1.05
1.10
1.15
1.20
1.25
1.30
1.35
1.40
1.45
1.50
1.55
1.60
1.65
1.70

71 of 73
APPENDIX 6

Line Width Variation Between Artwork and Final Etched Panel

Pretreatment Prior to Lamination
The copper surface prior to lamination has chemicals that will cause a strong
lock-in adhesion of the resist.
Chemicals include:

Copper oxides
Cu2O, CuO
Sulphur compounds from anti-tarnish formulation
Nitrogen compounds

Corrective Action: Ensure surfaces are thoroughly clean and dry prior to
lamination.
Lamination
Too high a temperature causes some heat polymerisation of the PHOTEC
polymer.
Corrective Action
Ensure that the surface temperature of the panels immediately after
lamination is between 40-60 oC. Adjust hot roller temperature and/or speed of
lamination in order to achieve this.
Cooling After Lamination
Boards remain at elevated temperature for a prolonged time after lamination.
Stacking the boards may create a large thermal mass, causing the boards to
cool slowly.
Corrective Action
To achieve a rapid cooling rate after lamination, rack panels one centimetre a
part. Use refrigerated air equipment to cool panel.

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Extended Time Between Lamination and Exposure
The chemical bond between the resist and copper will increase with time. This
will interfere with the development mechanism.
Panels are held too long without cover.
Corrective Action
Ensure panels are exposed as quickly as possible after lamination. If panels
are held more than 24 hours between lamination and exposure cover panels
with black polyethylene film.
Dry film photoresists are sensitive to a white light wavelength (yellow lights
will emit this light as well). Dry film photoresists will not develop if exposure to
light energy is greater than 2,8 mJ/cm2 and becomes more difficult if exposure
is 0-2,8 mJ/cm2.
Exposure
If the exposure temperature is too high, migration of the photoinitiators along
the path of the exposed areas will result. This may lead to partial exposure of
the resist. Due to refractive index, off contact exposure will cause increases in
line width.
Corrective Action
Ensure that the exposure equipment interior cooling system is switched on
and is effective. Panel temperature during exposure should not be higher than
30 oC.
Ensure that phototools are in direct contact with the photoresist.
Ensure that any protective film on the phototool does not have a refractive
index that will cause light scattering.
Cooling After Exposure
If panels are warm after exposure the migration of photoinitiators will continue
along the path of the exposed areas. This will lead to exposure of the resist
outside the opaque areas of the phototool.
Corrective Action
Rapid cooling of the panels after exposure is required. Ensure that the
polyester protective foil is not removed for a prolonged period prior to
development.

73 of 73
Development
The development mechanism is a diffusion controlled process. The pressure
within each spray bar of the nozzle should be a minimum of 1,5 Bar. The
pressure applied to the surface of the panel will depend upon:

Equipment design
Type and condition of pumps
Height of nozzle above panel surface etc.

Overall correct development conditions are essential in order to reproduce

etched tracks equal to artwork.
Corrective Action
Check:

Actual development solution temperature

temperature on the control module

Resist loading in the development solution to ensure it is below 0,2

m2/litre

Nozzle condition. Replace worn or blocked nozzles

Speed and rotation of pump

Solution volume output from pump. Replace worn impeller and/or

impeller housing

against

indicated

Water Rinsing After Development

Rinsing after development is an integral part of the development mechanism.
Inadequate rinsing may leave resist alongside the exposed resist, which in
turn will result in under etching.
The volume of water, spray pressure, temperature and water hardness are allimportant factors. Recommended water rinsing time should be at least 50% of
the development time. Too soft water will not stop the development action
and may lead to poor rinsing of development resist.
Corrective Action
Check:

Water spray pressure is greater than 1,2 Bar

Water temperature is between 12 and 25 oC

Hardness of water is 8-12 DIN

74 of 73
Drying After Development
If panels are stacked after development and prior to etching, ensure that
panels are completely dry and cooled to room temperature prior to stacking.
Etching
The etching stage may produce incorrect line width dimensions if the
parameters are not controlled correctly.
Corrective Action
Ensure that the correct chemical composition of the etchant is attained.
Ensure that the Oxidation-Reduction Potential is 540-600mV.
General
Ensure that the photoresist is used on the First-in First out basis and that it
is stored under the correct environmental conditions, i.e. temperature 5-20 oC,
relative humidity 40-60%.