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OrmeSTAR Ultra - The organic metal nanofinish

Article  in  Circuit World · February 2010

DOI: 10.1108/03056121011015059

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 OrmeSTAR™ Ultra – The Organic Metal Nanofinish

Dr. B Wessling, Dr. M Rischka, Dr. J Posdorfer

Enthone Nano Science Center – Ormecon GmbH, Ammersbek, Germany

Abstract

Purpose - The purpose of this paper is to introduce a new class of surface finishes –
Nanofinish – as an alternative to current final surface finishes.

Design/methodology/approach – This Nanofinish utilises Ormecon’s

nanotechnology and is based on a new formulation of the Organic Metal. The final
surface finish is an approximately 50 nm thin permanent layer, consisting of a complex
between the Organic Metal (OM) and silver (Ag). Panels finished with OrmeSTAR
Ultra show excellent solderability in spite of a low layer thickness and therefore offer
significant advantages over existing surface finishes.

Findings – This Nanofinish has proven to be a competitive alternative to current final

finishes with excellent properties for soldering applications. OrmeSTAR Ultras new
nano technology can also significantly to improve the environmental and economical
consequences of solderable surface finishing.

Keywords Organic Metal, Nanofinish, Environment, Printed Circuits, solderable

surface finish

Paper Type Technical Paper

1. Introduction

The organic metal (OM) is an advanced form of conductive polymers which has
metallic properties even though it is characterized as an organic compound. The
material is composed of carbon (C), hydrogen (H), nitrogen (N), oxygen (O) and
sulphate (So) and is synthesized and dispersed in the form of 10 nanometer (nm)
small primary particles [1]. A strong effect in the prevention of copper (Cu) oxidation [2]
was discovered many years ago. For over 10 years the material has been
commercially used for finishing printed circuit boards as a predip in Ormecon’s
immersion tin process—ORMECON CSN. In this process, the organic metal is used
as the Cu surface preparation predip prior to the immersion tin (Sn) deposition [3].

The process is well established and widely used in the printed circuit board (PWB)
industry as one of the top quality alternative finishes required for lead-free electronics
manufacturing. The organic metal predip is applied as a 80 nm thin adsorbed
layer—causing the selective formation of Cu (+1) and a passivation of Cu. In addition,
it takes part as a catalyst to provide electrons for Sn (2+), which is subsequently
deposited onto the Cu.

It has been the object of Ormecon’s research for more than 10 years to provide a
solderable surface finish for PWBs which would mainly contain just the Organic
Nanometal while offering an excellent solderability performance. A first process
version in which the OM would be the final surface finish (no longer the predip) i.e. a
nano finish - was presented for evaluation three years ago [4]. The surface finish was
already suitable for lead-free soldering, but not stable enough with respect to
discoloration. The new nanofinish generation, based on the organic metal / silver (Ag)
complex, shows high performance with regard to ageing resistance, discoloration and
solderability.

2. Morphology and Deposition Reaction

Investigations into the deposition and morphology properties show that the surface
finish is a thin layer (50 – 60 nm average thickness) consisting of an Organic Metal /
silver nanoparticle complex where the silver content is equivalent to a nominal
thickness of 4 – 5 nm.

2.1 Coulometric Investigation

The electrochemical investigation by a galvanostatic coulometric measurement (GCM)

shows that the organic metal based OrmeSTAR Ultra has formed a new type of
complex on the copper surface (Figure 1). The potential at which this complex is
oxidized is significantly different from Ag on Cu alone suggesting the formation of an
Organic Metal / silver complex.
Figure 1: Potential-time-curves for Cu, Ag coated on Cu by immersion and Nanofinish.

The deposition reaction properties were investigated in dependence on the immersion

time in the organic metal / silver plating bath (Figure 4). The results show that a
minimum immersion time is necessary to obtain complete coverage of the copper
surface which is necessary for its passivation. The potentials indicate that the amount
of free copper surface (potential at ~ - 0.35 V) decreases slowly with short dipping
times and the highest coverage rate occurs between 40 and 60 seconds immersion
time. After 60 seconds, the rest of the free copper surface is coated slowly. At about
90 seconds no (electrochemically accessible) free copper is detectable
the
deposition reaction is complete and the copper surface is passivated.

Figure 2: Potential-time curves for a copper surface being coated with the organic
metal / silver nanofinish for different immersion times.

The nature and formation of the OM-Ag nanoparticle complex has been investigated
in more depth which was published in the proceedings of the ICSM 20085.
2.2 XPS Investigations

XPS depth profiles of copper and silver on the organic metal based nanofinish copper
surfaces show that the Ag is only nominally detectable to a depth of 2 to 3 nm —
before and after reflow. From the XPS data it was determined that the volume of the
layer is around 90% organic (30% by weight) with a nominal silver layer thickness of
only a few nm.

Figure 3: XPS depth profile for an OrmeSTAR Ultra surface

At the outermost surface, the Ag:Cu ratio changes only slightly during the reflow
process (becoming smaller). But, from a depth of about 2 nm on, no change in the
ratio is detected after the reflow process. No Ag migration could be detected — the Ag
seems to be immobilized in the complex with the OM.

Even more interesting is the ratio of metallic to oxidized copper atoms in the outer
surface of the pad before and after reflow as shown in Figure 4. Only up to max 2 nm
in depth, a few percent of the Cu atoms are oxidized, already 2 nm deep, 100% of the
Cu atoms are in metallic state. This ratio did not significantly change during the reflow
process which proves that the surface finish effectively prevents the oxidation of
copper (Figure 5).
Figure 4: Ratio of metallic to oxidized copper in the fresh sample (surface).

Figure 5: Ratio of metallic to oxidized copper in a reflowed sample (surface).

2.3 SEM Investigation

Figure 6 shows a scanning electron microscopy (SEM) image of copper pad of a PWB
after treatment with OrmeSTAR Ultra. The image shows that the 50 nm particles of the
OM-Ag complex are preferably located on the phase boundaries (active sites) of the
Cu crystallites. Most of the visible area is Cu surface. However due to the properties
of the OM-Ag complex the copper surface is electrochemically protected.
Figure 6: SEM image of a PWB after treatment with the OM-Ag plating bath

Further investigations with a high resolution SEM6 confirmed that the morphology
consists most likely of OM-Ag nanoparticles which are scattered on the Cu surface
(phase boundaries). At high magnification, even smaller particles are detectable (~ 20
nm, cf. Fig 7) which confirmed that the coverage of Cu surface is denser but still
scattered and discontinuous. It was also possible to see in element mapping trials that
the elements S, O and Ag were found on the same locations supporting the presence
of an OM-Ag complex.

Fig 7 High resolution SEM at 250,000 times magnification showing around 20 nm fine
OM-Ag nanoparticles scattered on the Cu surface in the surface apparently uncoated
between larger nanoparticles, cf. Fig 6.
2.3 Kelvin Potential

The surface potentials of copper, oxidized copper, silver on copper after immersion
and the organic metal/silver nanoparticle finish on copper after immersion were
determined using a scanning Kelvin probe (SKP, UBM Messtechnik GmbH). The
Kelvin potential is a very reliable indicator of the sensitivity of a surface towards
oxidation. Figure 8 shows a copper surface treated with organic metal/silver
nanoparticle finish just after finishing.

Figure 8: Copper surface treated with the organic metal/silver nanoparticle finish.

The Kelvin potentials of various treated and untreated copper surfaces are
summarized in Table 1. The new nanofinish, composed from an Organic Metal-Ag
nanoparticle sized complex, reaches almost the same potential as a pure Ag layer
which contains more than 100 times more silver.

Surface Kelvin potential [mV]

Cu (pure, unoxidized) 70
Cu oxides 150 – 180
Cu treated with OrmeSTAR Ultra 320 – 340
(50 nm layer, containing nominally 4 nm Ag)
Cu treated with immersion silver 400
(500 nm layer)
Table 1: Kelvin potentials of various surfaces.
3 The OrmeSTAR Ultra Process

Using the knowledge from the investigations the Organic metal / silver plating bath
was developed into a full final finish process for PWB applications. The process starts
with a combination of a modified acid cleaner, already containing some OM, and a
specially adapted micro etch. A predip—conditioning for up to 120 seconds depending
on Cu surface type—prepares the boards for the active bath (e.g. OMN 7200,
depending on the grade, 35°C for 90 seconds). An optional post dip also contains the
Organic Metal and enables easier and better handling of the PWBs by allowing a
quick and residue free removal of the rinse water. A final rinse and a dryer complete
the process (Figure 9).

Organic
Rinse

Rinse

Rinse

Rinse

Dry
Acid Micro Cond. Metal Post-
Cleaner Etch Bath Dip

Figure 9: Process scheme for OrmeSTAR™ Ultra.

Detailed continuous use studies of the OrmeSTAR Ultra Nanofinish process have
shown that under different scales the process is surprisingly stable. The process
window (determined by bath temperature and bath components concentration) is
much wider than with any other surface finish process. The key additives (OM and Ag,
acidity etc) can easily be analyzed and monitored, and the replenishment scheme is
simple.

However it should be noted, that the Nanofinish process OrmeSTAR Ultra requires a
clean Cu surface which in case of intolerable organic contaminations resulting from
previous PWB manufacturing steps can be achieved by additional pre-cleaning steps
for which Enthone provides the appropriate cleaners.

4. Properties of the OrmeSTAR Ultra Surface Finish

4.1 Visual Appearance

Figure 10 shows a PWB before treatment, directly after plating the surface with the
organic metal based nanofinish and after treatment and aging. When plating with
OrmeSTAR Ultra the normal appearance of the panel surface is an even silvery colour
with some slight copper hue. After reflow and aging the surface finish may darken
slightly but it remains even. It should be noted that the silvery colour does not result
from a visually detectable coverage of the Cu surface by silver – for this the Ag
amount with nominal 3 – 4 nm thickness only (which is not present as a homogeneous
layer at all); however our interpretation is that the silvery colour results from a change
in the response mode of the metal surface to the influx of photons, altering the
absorption and reflection of the photons on the metal surface which after finishing with
the OM-Ag complex has a different surface potential and hence a different interaction
with photons.

Figure 10: No discoloration after reflow.

4.2 Solderability Performance

Thermal aging was performed to simulate soldering and storage conditions. To

simulate typical soldering conditions, test panels on which the organic metal based
nanofinish had been deposited under standard conditions, were tempered up to four
times in the RO 300 FC N2 reflow oven from Essemtec. A lead-free soldering profile
was chosen with a peak temperature ~ 250°C. To simulate storage conditions, other
test panels were aged 4 hours at 155°C. The performance of copper surfaces treated
with organic metal / silver nanofinish is compared before and after reflow in Table 2.

Process Reflow cycles Wetting angle Wetting angle after ageing

[°] at 155 °C for 4 h [°]
OrmeSTAR Ultra 0 15-20 25-30
1 20 - 25 25 – 30
2 25 - 30 25 – 30
3 20 - 30 30 – 35
4 30 - 35 30 – 40
Table 2: Wetting angles before and after the reflow process for OrmeSTAR Ultra

The organic metal based nanofinish does not show any discoloration during reflow
(Figure 10) and the wetting behaviour, according to wetting balance studies, is
superior to any metallic surface finish (Table 2). Practical tests in PWB manufacturing
and in assembly facilities have confirmed these results.
These solderability results have been confirmed by external evaluations.

A big Chinese OEM in the telecommunication sector evaluated OrmeSTAR Ultra in a

9 month long project (first phase) for its electrical and soldering properties. The results
showed that the surface finish did not discolour even after 7 reflow steps (lead free
conditions). The solder spread properties was outstanding and the PTH wetting had a
0% failure rate even after 5 reflow steps. The solder joint properties (IMC) were
normal and the shear strength was above specification and comparable to metallic
finishes.

The results of the electrical tests were also excellent. The surface resistance with a
value of ~ 12 mOhms is considerably lower than the value for ENIG (18 mOhms). The
signal gain, loss and efficiency are comparable which will improve single carrier wave
performance. In an IC test only 2 out of 21 600 samples failed. OrmeSTAR Ultra
behaved in fact like a metallic finish.

In the USA, the „New England Lead-Free Consortium“ carried out a broad assembly
study with four different finishes: LF-HASL, ENIG, OSP and OrmeSTARTM Ultra. The
first results were published in September 2008, a full report can be found in7. They
tested a number of assembled components with different solder pastes and found that
for the SMT components (surface mount technology, 21 per board) OrmeSTAR Ultra
had the lowest number of defects and performed better than ENIG (Figure 11). For the
THT (through hole technology, 866 each board) assembly the results for OrmeSTAR
Ultra were comparable to ENIG (Figure 12).
 SMT Assembling
Number of defects
25

20
Number of defects

15

10

0
SAC305 NC1 SAC305 NC2 SAC305 OA Tin Lead NC

SMT

ENIG HASL LF OSP (halogen free) OrmeSTAR Ultra

Figure 11: Results of the SMT assembly

THT Assembling
Number of defects
600

500
Number of defects

400

300

200

100

0
SAC 305 SN100C 1 SN100C 2 Tin Lead

THT
ENIG HASL LF OSP (halogen free) OrmeSTAR Ultra

Figure 12: Results of the THT assembly

4.3 Microvoids & Solder Joints

With immersion Ag surface finishes, micro voids may occur and are an object of broad
investigations and considerations. With the organic metal based nanofinish, no micro
voids have been observed in cross section and x-ray investigations (Figure 13).

Figure 13: Cross section and XRF show no micro voids.

An external analysis [8] showed that the lead-free-Sn solder joints (ball grid array or
BGA pads) with the OrmeSTAR Ultra surface finish are of a high quality. The
nanofinish solder joints are expected to show long term reliability.

Figure 14: Perfect solder joint.

4.4 Press Fit Technology

The press fit properties of the OrmeSTAR Ultra surface finish were tested by Erni in
Germany with two types of press contacts: 0.6 & 1.0 mm holes. The connectors are
pressed into the holes and the force is measured along the path of the connector. The
force / path diagrams are shown in figures 15 & 16 and selected values are given in
table 3. From the experience obtained by Erni, if the values for a surface finish are
within the minimum / maximum range it is suitable for press fit applications.

OrmeSTAR Ultra shows the same behaviour as immersion tin which is most widely
used for press fit applications, and has a significantly higher press force than e.g. OSP.
Generally the OrmeSTAR Ultra technology is suitable for press fit assembly.
 Connector 1
6000
CSN Classic WR

OrmeSTAR Ultra
Press Force [N]

4000

2000

0
0 1 2 3 4 5
Path [mm]

Figure 15: Force / path diagram for connector 1

Connector 2
6000
CSN Classic WR

OrmeSTAR Ultra
Press Force [N]

4000

2000

0
0 1 2 3 4 5
Path [mm]

Figure 16: Force / path diagram for connector 2

 Press Force [N]
Surface Finish pass / fail
min max Fmax for SF
Connector 1
CSN Classic WR 4021 pass
1800 7680
OrmeSTAR Ultra 4055 pass
Connector 2
CSN Classic WR 5708 pass
2310 6930
OrmeSTAR Ultra 5959 pass
Table 3: Press fit data for the surface finishes

5. Environmental Impact of OrmeSTAR Ultra

The increasing costs of raw materials and energy as well as environmental regulations
and economical considerations, are driving the electronics industry to find alternatives
to the current surface finishes for PWB manufacture. OrmeSTAR Ultras new nano
technology can significantly to improve the environmental and economical
consequences of solderable surface finishing.

An external investigation carried out on behalf of the German Federal Environmental

Agency (FEA) [9] showed that compared to commercial surface finishes, Ormecon’s
Organic Metal nanotechnology in the form of OrmeSTAR Ultra can reduce energy
consumption by 50 – 75% or even in some cases by 93% in comparison to currently
used surface finishes. Similar savings were also determined for CO2 emissions, raw
material demand, and the water consumption for the OrmeSTAR Ultra process can be
reduced by 30 – 75%. For the study all aspects of the process were considered
including raw material extraction and manufacturing as well as water and energy
requirements (Figure 17). The values highlighted in the following table and figures are
calculated for 1000 m² PWB with a Cu area of 25 %.
Figure 17: General considerations for the FEA study

5.1 Material Consumption

This amount of material involved in plating 1000 m² PWB with OrmeSTAR Ultra is
shown in figure 18. The data includes all parts of the process including material
extraction, refining and product manufacturing. Due to the low layer thickness and only
nano amounts of Silver metal OrmeSTAR Ultra offers significant advantages in
material consumption compared to conventional surface finishes. As expected ENIG
shows the highest material demand and OrmeSTAR ultra with 0.077 kg has the lowest
value, even lower than OSP (0.23 kg).
 Material Demand

40000

35000
Consumption [kg / 1000 m²]

30000

25000

20000

15000

10000

5000

0
HASL ENIG Im Ag Im Sn OSP OrmeSTAR
Ultra

Figure 18: Comparison of Material Demand for PWB Surface Finishes

5.2 Energy Consumption

This amount of energy required to plate 1000 m² PWB with OrmeSTAR Ultra has also
been determined and is shown in figure 19. The data includes all parts of the process
including material extraction, refining and product manufacturing. Due to the low layer
thickness OrmeSTAR Ultra offers significant advantages in material consumption
compared to conventional surface finishes. As expected ENIG shows the highest
material demand and OrmeSTAR ultra has the lowest value, even lower than OSP.
 Electrical Energy Consumption

1600

1400 vertical
horizontal
Electrical Energy Consumption [kWh / 1000 m²]

1200

1000

800

600

400

200

0
HASL ENIG Im Ag Im Sn OSP OrmeSTAR
Ultra

Figure 19: Comparison of Energy Demand for PWB Surface Finishes

5.3 Water Consumption

This amount of water required to plate 1000 m² PWB with OrmeSTAR Ultra is shown in
figure 20. The data shows that OrmeSTAR Ultra has the lowest water demand of all
surface finishes. As a consequence, also waste water is minimal, and the Nanofinish
waste water does not contain any specially hazardous or regulated substances.

Water Consumption

6
Vertical
Horizontal

5
Water Consumption [m³ / 1000 m²]

0
HASL ENIG Im Ag Im Sn OSP OrmeSTAR Ultra

Figure 20: Comparison of Water Demand for PWB Surface Finishes

5.4 Greenhouse Potential

This calculated value indicates how each surface finish potentially contributes to the
Greenhouse Effect and is given as a CO2 equivalent. Due to the high values calculated
for ENIG (36 657 kg CO2 Aq) and to allow a comparison of the other surface finishes it
was not added to Figure 21. The data shows that OrmeSTAR Ultra has the lowest
Greenhouse Potential of all surface finishes.

Greenhouse Potential

800

700
Greenhouse Potential [kg CO2 Aq / 1000 m²]

vertical
600
horizontal

500

400

300

200

100

0
HASL Im Ag Im Sn OSP OrmeSTAR Ultra

Figure 21: Greenhouse Potential for PWB Surface Finishes

Calculated Demand and Possible Savings* per 1000 m² PWB

Surface Finish Material Energy Water
Demand [kg] Saving* Demand [kwh] Saving* Demand [m³] Saving*
OrmeSTAR Ultra 0.077 -- 95.4 -- 1.47 --
HASL 10 409 > 99 % 400.5 ~ 76 % 3.52 ~ 58 %
ENIG 36 523 > 99 % 1410.1 ~ 93 % 5.87 ~ 75 %
Im Ag 1 199 > 99 % 443.9 ~ 78.5 % 1.50 ~2 %
Im Sn 3 481 > 99 % 377.6 ~ 75 % 5.14 ~ 71 %
OSP 0.229 ~ 97% 176.2 ~ 46 % 2.2 ~ 33 %

Table 4: Data calculated from the FEA study; *”Saving” is meant to show how much
the Nanofinish OrmeSTAR Ultra can save compared to the respective other surface
finish
 6. Summary

With the organic metal based OrmeSTAR Ultra nanofinish, a nanoparticulate complex
between the OM and Ag is described for the first time. Although it does not form a
continuous nanolayer, the polymer completely and effectively electrochemically
shields the Cu and prevents the substance from being oxidized after at least four
lead-free reflows. Aging resistance and wetting (soldering) performance is excellent
and enables the replacement of established PWB surface finishes. The surface finish
also has significant environmental and economic advantages compared to other
surface finishes.

The OrmeSTAR Ultra process allows original equipment manufacturers (OEMs),

assemblers and PWB manufacturers to produce boards featuring higher productivity,
lower failure rates and, most importantly, lower costs and lower environmental impact.

References
1
B. Wessling, Handbook of Conducting Polymers (T. Skotheim, R. L. Elsenbaumer, and J.
R. Reynolds, eds.). Dekker, New York, (1998).
2
B. Wessling, Adv. Mater. 6, 3, 226, (1994).
3
www.ormecon.de (ORMECON CSN, technical information).
4
N. Arendt, C. Arribas, J. Posdorfer, M. Thun, B. Wessling, OnBoard Technology, 12,
(April 2006).
5
J. Posdorfer, B. Wessling, oral presentation on the International Conference on Science
and Technology of Synthetic Metals, Brazil 2008, Proceedings being published in
Synthetic Metals (Elsevier)
6
Unpublished results, provided by E. Kuo, Enthone Taiwan
7
a) http://www.smta.org/files/Gregory_Morose_SMTA_IEEE_July_2009.pdf
b)http://www.smta.org/files/Farrell_Robert_Lead_Free_Assembly_Nano_SMTA_IEEE_July_14
_2009.pdf
8
Dr.-Ing. Manfred Deger, Analytik - Labor – Possendorf, (June 2007)
9
Relief Effects for the Environment through Nanotechnological Processes and Products –
Bremen University and the Institute for Ecological Economy Research in Leipzig – Study
on behalf of the German Federal Environment Agency

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