Accepted Manuscript

Title: Incorporation of Tin on Copper Clad Laminate to

Increase the Interface Adhesion for Signal Loss Reduction of
High-frequency PCB Lamination

Authors: Chong Wang, Na Wen, Guoyun Zhou, Shouxu

Wang, Wei He, Xinhong Su, Yongsuan Hu

PII: S0169-4332(17)31373-9
DOI: http://dx.doi.org/doi:10.1016/j.apsusc.2017.05.061
Reference: APSUSC 35996

To appear in: APSUSC

Received date: 16-1-2017

Revised date: 16-4-2017
Accepted date: 7-5-2017

Please cite this article as: Chong Wang, Na Wen, Guoyun Zhou, Shouxu Wang, Wei He,
Xinhong Su, Yongsuan Hu, Incorporation of Tin on Copper Clad Laminate to Increase
the Interface Adhesion for Signal Loss Reduction of High-frequency PCB Lamination,
Applied Surface Sciencehttp://dx.doi.org/10.1016/j.apsusc.2017.05.061

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 Incorporation of Tin on Copper Clad Laminate to Increase the

Interface Adhesion for Signal Loss Reduction of High-frequency

PCB Lamination

Chong Wang1,2, Na Wen1, Guoyun Zhou1, Shouxu Wang1, Wei He1,2*, Xinhong Su3, Yongsuan Hu3

(1State Key laboratory of Electronic Films and Integrated Devices, University of Electronic Science and

Technology of China, Chengdu 610054, P. R. China;

2
Guangdong Guanghua Sci-Tech Co., Ltd, Guangzhou, P. R. China;
3
Zhuhai Founder Sci-Tech High-Density Electronic Co., Ltd, Zhuhai, P. R. China)

17 
 
Ga

NEAP

NEAP  Brown Oxide

Copper
Surface

Insert
Loss of

Highlights：
1. We substitute the copper surface of PCB by tin to decrease the IEP (isoelectric point) and to

increase the peel strength of copper foil with prepregs, which is called as NEAP (Non-etching

adhesion process).

2. The NEAP creates a higher peel strength with smooth surface in compatibility with high

frequency signal transmission, compared with the traditional brown or black oxidation method by

copper etching.

18 
 
3. The actual composition of tin to increase the peel strength was studied in mechanism.

Abstract. A novel method of improving the adhesion between copper and prepreg in high frequency

PCB was proposed and studied in this work. This process which aimed to decrease the IEP

(isoelectric point) of the copper to obtain higher adhesion, was achieved by depositing a thin tin layer

with lower IEP on copper. It was characterized by scanning electron microscopy (SEM), 3D

microscope, peel strength test, X-Ray thickness test, grazing incidence X-ray diffraction (GXRD),

X-ray photoelectron spectroscopy (XPS), Agilent vector network analyzer (VNA), which confirmed

its excellent adhesion performance and outstanding electrical properties in high-frequency signal

transmission compared with traditional brown oxide method. Moreover, the mechanism of achieving

high adhesion for this method was also investigated.

Keywords: PCB lamination, NEAP (Non-etching adhesion process), High-frequency, IEP

(Isoelectric Point)

1. INTRODUCTION

High-frequency signal transmission needs the formation of fine copper lines in high-density

interconnection PCB (Printed Circuit Board).[1] However, a traditional micro-etch treatment

including brown oxide or black oxide creating a rough copper surface provides the essential

mechanical bonding to prepreg with its micro-anchor to ensure excellent thermal reliability for

PCB.[2][3] It is believed that this technique will eventually encounter obsoletes in the future PCB for

the applications with high frequency over 25 GHz or in THz, including the next 5G communication,

GPU (Graphics Processing Unit), and THz communication under the high signal transmission loss.

In high-frequency, an AC signal primarily flows nearer to the outside surfaces of a copper conductor

rather than through the entire cross section of the conductor, i.e., a phenomenon called as skin effect.

As frequency increases, the skin effect becomes more pronounced.[4][5] A. Zee and R. Massey

19 
 
conducted a simulation of signal loss, and obtained a result that the signal loss of track treated with

etch-based treatment was 14% more than smooth track, actually the actual measurement showed

more. A. Deutsch also pointed out the dedication of surface roughness to signal integrity was

significant. [6][7] For this consideration, micro-etched or roughened surface is destined to cause signal

loss, resulting in signal integrity transmission problems. Moreover, smoother surface for signal

transmission is required for high resolution ultra-fine lines towards 8 μm in the near future

technology for PCB. A series of problems including low adhesion with substrate, easy presence of

short or open circuits are inevitable, in case of the roughness up to 2~3μm under brown oxidation or

black oxidation method for these ultra-fine lines.[8] Particularly, high frequency signal suffers a great

loss in the long threads signal transmission. Consequently, researchers for high frequency PCB are

turning their eyes to making smooth surface conductors with maintained adhesion between the

copper and prepreg.

Generally, copper and prepreg bonding enhancement should be provided through mechanical

bonding or chemical bonding or both.[9]To maintain a smooth and consistent track surface, the

micro-etch process for mechanical bonding, such as brown and black oxidation methods, is prompted

to be replaced by chemical interaction, namely, non-etching adhesion process (NEAP).[10] The

chemical interaction between metal and polymer is described by the interaction of a metal oxide with

a polymer, which is typified as acid-base chemistry. [11][12]To predict the probability of the interaction

to occur, equilibrium constants  for acid-based interactions can be expressed in terms of the

strength of the acid K for polymer and the IEP (Isoelectric Point) for metal, which is indicated as:

=pK-IEP [9] (1)

The  with high value predominates the strong interaction between polymer and metal surfaces,

resulting in strong coordinative covalent bonds between the adherend and adhesive. As shown in

equ.(1), while the adsorption of hydroxide ions on a metal surface covered by a thin oxide layer,

metal with lower IEP should effectively achieve higher bonding strength with a fixed polymer

20 
 
through Van der Waals' force and the hydrogen bond.[13]

The goal of the work is to find a metal conversion of low IEP to enhance the bonding strength

between copper laminate and prepreg. Tin is an excellent metal with low IEP of 4 and other

advantages such as low-cost, easy fabrication, and sufficient compatibility with PCB

production.[14][15] Tin was deposited on copper laminate by electroless process in order to replace the

copper surface (IEP=9) with lower IEP surface.[16] Significant improvement for the adhesion strength

between the copper and prepreg was found. Accordingly, PCB achieved a superior adhesive and

exceptional thermal reliability by tin surface conversion without changing the track profile. Both

signal transmission integrity and fine line fabrication benefited from this surface treatment method.

2. EXPERIMENTS

Process of Copper surface conversion. Copper clad laminates with copper foils of 18 μm in

thickness were used to bond with pregreg. The schematic diagrams of NEAP process on copper

surface were illustrated in Fig. 1. In a typical treatment process, the organic contaminations such as

dry film resist and oily fingerprints were removed in an alkaline cleaning solution (NaOH 60g/L,

NaCO3 30g/L, Na3PO420g/L). It then was followed by the removal of other heavy oxides,

anti-tarnish layers or detergents by rinsing in the acid cleaning solution (5% H2SO4 solution that

added 5% concentrated degreasing solution). The copper clad laminate should be washed at least 3

times in deionized water after each step above-mentioned. Subsequently, the surface of laminate was

coated with a very thin tin by soaking in the tin eletroless-plating solution (SnCl2•2H2O 20g/L,

SC(NH2)2 75g/L, HCl 80g/L, NaH2PO2•H2O 30g/L, surfactant 1g/L and stabilizer 1g/L). The tin

reduction time was controlled from 40s to 400s for its affinity to the plated-tin thickness. Activating

process is necessary for converting tin metal by the mixing of NaNO2 solution with dilute alkali lye

to achieve lower IEP.

Characterizations. The peel strength of tin-coated copper with pregreg (PI pregreg) was carried out

after the lamination under IPC-TM650 standard at a peeling rate of 10 mm/min with a peel tester,

21 
 
 [17]
PT-800. To evaluate the effectiveness of NEAP, copper micro-etched using brown oxidation was

measured in peel strength by the same process above. The copper surfaces processed by NEAP and

brown oxidation were characterized by scanning electron microscopy (SEM, JEOL JSM-6060) for

morphology observation and by 3D microscope (OLYMPUS, LEXT OSL4000) for roughness

measurement, respectively. The plated thickness of tin on copper for NEAP was inspected by X-Ray

thickness tester (Fisherscope X-Ray XDLM) and the tin structure before lamination and after

lamination were analyzed by grazing incidence X-ray diffraction (DX-2700, Dandong fangyuan

instrument Co., LTD) with Cu Kα radiation (Bede, D1 System, λ=1.5418 × 10−10 m). X-ray

photoelectron spectroscopy (XPS, ESCA2000, VG Microtech) was designed to detect the chemical

compositions of the separated sides after peeling test for copper and PI, determining the broken

positions in peeling process. Furthermore, the high frequency signal loss attenuation was performed

by taking S-parameter measurements in the range of 1 MHz~20 GHz using an Agilent vector

network analyzer (Agilent ENA Series Network Analyzer E5071C). The test structure vehicle is

presented in Fig.2, in which high frequency laminated copper clad (Panasonic M6) was employed as

its dielectric substrate.

3. RESULTS AND DISCUSSION

Surface characterizations.

The obtained surface morphologies for copper foil after NEAP process was characterized by SEM,

as shown in Fig. 3a. For comparison, copper foil processed with brown oxidation method was

presented in Fig. 3b. The copper surface etched by brown oxidation solution was clearly observed

with roughness of 2~3 μm in horizontal direction, which is required to enhance the adhesion by

physical interlocking mechanism in PCB lamination process. However, this rough characterization

was substituted by a smooth plated tin thin-film on copper after NEAP treatment. As observed on the

SEM, Corresponding 3D microscope images were taken to demonstrate their vertical patterns and the

surface roughness. The typical rough profile of copper foil processed by brown oxidation was

22 
 
revealed, as shown in Fig. 3d, to have ridges with dimensions on the order of 2~3 μm in width by

approximately 2~3 μm in depth. This feature was also affiliated by some smaller irregular shapes,

sizes, and separations. It contributed the roughness in vertical direction producing a roughness of

0.479um in the parameter Ra. By contrast, the sample with NEAP obviously keeps a relatively

smooth surface (Fig. 3c), in consistent with the image observed from SEM in Fig. 3a. Accordingly,

the roughness Ra was calculated to be 0.236 by nanoscope software. It demonstrated that when

copper lad with lines was used as basic substrate, the technique of NEAP shows an excellent

feasibility without any apparent morphology defect, indicating the dominant superiority in

high-frequency signal transmission compared with copper roughening surface treatment.

Insertion Loss

It was known that “skin effect” is more pronounced as the high-frequency signal increases,

leading to a severer signal loss over 1 GHz. The insertion loss (S parameter) to clarify the signal loss

of conductive lines treatment by NEAP and brown oxidation was shown in Fig. 4. This is no obvious

difference of signal loss for these two methods for the loaded frequency lower than 5 GHz. Higher

signal loss differences of 1.4 dB/m and 4.23 dB/m at the frequency of 10 GHz and 20 GHz

respectively, was contributed by brown oxidation in comparison with NEAP. The obvious

discrepancy in signal loss can be accounted for the surface roughness differences, in which the

roughened surface for brown oxidation produce higher signal loss due to “skin effect”. Accordingly,

the copper foil treated by NEAP to fabricate conductive lines can effectively reduce the signal loss,

and more significant at higher frequency.

Effects of immersion time on adhesion

SEM images in Fig. 5 showed the surface morphologies of copper foil at varied immersion

times of 0s, 40s, 80s and 120s in the tin replacement solution. The common low surface profile was

observed at the bare copper of FR-4 copper clad sample in Fig. 5a. After immersed for 40 s, the

tin-plated copper showed a global homogeneous copper surface duplication (Fig. 5b). It is reported

23 
 
that the tin-reduction reaction on copper surface consists of two stages, i.e., the replacement of

copper by tin and the continuous growth of tin by tin self-reduction.[18] The surface morphology

demonstrated a typical tin replacement reaction at the first 40 s. At the continuous immersion to 80 s,

the tin crystalline grain is very notable, indicating the tin replacement reduction was finished and the

self-reduction process has begun (Fig. 5c). When the sample was immersed another 40 s in tin

solution, the lager-sized tin crystalline grain was formed, as shown in Fig 5d.

The thickness of as-plated tin on copper foil varied with depositing time was shown in Fig. 6a. The

time was in the range of 0~200 s. The thickness of the tin layer is only around 0.16μm at duration of

40 s, whereas the immersion time of 200 s increased the thickness to 0.34μm, indicating a thicker

coating with more displacement time. It is notable the curve in Fig. 6a is steeper at the early time of

deposition. This implies that the deposition rate is relatively high during the initial stage and

gradually slows down with extended deposition time.

The corresponding peel strength in Fig. 6b showed the relation of adhesion with the tin thickness

increasing. The tin deposit on copper indicated an obvious improvement in comparison with bare

copper. The peel strength of bare copper foil is 0.43 N/mm. However, the peel strength of a finished

PCB should be higher than 0.5  N/mm according to the IPC standard. After immersed for 80 s, this

value is increased to 0.71 N/mm. The highest peel strength was test to be shown at 0.89 N/mm,

which was contributed by the as-plated tin with thickness around 250 nm or with immersion time of

120 s. At this specific point, the tin crystalline grains begin to be formed as shown in Fig. 5d. If the

crystalline grains continue to grow bigger when the immersion time was prolonged, the adhesion

between copper and prepreg was lowered down. Therefore, to optimize the adhesion for copper with

prepreg, the tin reaction time should be set at about 120 s.

In the case of solid–liquid (or prepreg) contacts, their interface adhesion has been usually

attributed to surface roughness or to chemical interaction.[19] The peel strengths between copper foil

and prepreg without treatment and treated by NEAP and brown oxidation method were listed in Fig.

24 
 
6c., copper foil treatment is definitely requisite for obtaining high reliability of PCB lamination. For

both the NEAP and brown oxidation, the adhesive strength has demonstrable improvement (almost 2

times) in comparison with that without treatment. The NEAP produces a highest adhesion around

0.89 N/mm at the smooth copper foil plated a very thin tin film. NEAP slightly wins out over the

brown oxidation method of producing a chaotic surface with high roughness for adhesive strength.

Obviously, NEAP achieved this excellent effectiveness by the chemical interaction of as-plated tin

and prepreg while brown oxidation method by physical interlocking.

Adhesion interface

The as-laminated copper with PI by NEAP included several peeling interface, such as

copper-copper, copper-tin, tin-tin, tin-PI and PI-PI. The excellent adhesion treated by NEAP was

expected to perform at the interfaces of copper-tin, and tin-PI, i.e., the peel position occurs at the

materials body of copper or PI.

Fig. 7 showed the optical and SEM images of the separated interfaces after peeling test. It is

observed that a delaminated thin-film attached on tin-plated copper foil. To demonstrate the adhesion

failure, Fig. 8 displays the XPS spectra of the separated PI part and copper part, respectively. The

spectra for PI part, as shown in Fig. 8, indicates the simple detection of elements of C and O, which

are the dominant components of PI. Corresponding elements such as Sn and Cu were not responded

in the XPS analysis. Moreover, the elements of Sn and Cu, which are dominant components of

copper part, did not provide the spectral responses in the XPS data either (Fig. 8). The detectable C

and O suggested that the PI was attached on the surface of tin-plated copper after peeling test, which

was observed in the aforementioned SEM images (Fig. 7b). Therefore, it can be concluded that the

delaminated position for NEAP sample was located at the interface of PI-PI. The delaminating

phenomenon was also verified by brown oxidation method. This showed NEAP like brown oxidation

can produce an excellent bonding for copper and PI prepreg, which outperforms the PI materials

body.

25 
 
Potential Mechanism

After NEAP process, the copper foils before and after laminated with PI as well as after

activated were analyzed by grazing incidence XRD with the incident angle of 1.5°. The results are

presented in Fig. 9. As shown in Fig. 9(a), the activation solution turned the tin into its oxides such as

SnO and SnO2, in which the tin position was not detected. To response the peel strength variation in

Fig. 6b, O content was analyzed by XPS (Fig. 9b). The spectra showed a clear correlation between

the peel strength and O content, in which high O content in Tin layer leads to high peel strength [20-28]

For that, the IEP of SnO and SnO2 was determined by measuring the zeta potential by means of the

electrophoresis and electro-acoustic methods. The IEPs of SnO and SnO2 calculated after
[7]
measurement were 6.1 and 4.3, respectively, where CuO was around 9.2. Therefore, It is

conducted that the peel strength enhancement was resulted from the very thin superficial metal

oxidation. In addition, features of CuxSny in the XRD indicates the deposited tin layer covered on

copper substrate with an excellent connection for the adhered layer.[29][30]

4. CONCLUSIONS

To achieve smooth copper foil surface bonding to prepreg for PCB interconnection, a new

surface treating method, called NEAP, was introduced by IEP mechanism. Due to the chemical

interaction, the sample of NEAP achieves higher peel strength of 0.89N/mm, whereas that of the

brown oxidation is 0.78N/mm under physical interlocking. This peel strength of 0.89N/mm was

contributed by the as-plated tin with thickness around 250 nm or with immersion time of 120 s, in

which longer or shorter immersion should decrease the peel strength. In fact, the peel strength

enhancement was attributed to high quantity of oxide tin. The peeling interface, verified by XPS, was

happened at the PI-PI, indicating the NEAP method yields a very high bonding force and hence can

replace the brown oxidation method. Besides that, the NEAP showed additional superiority in

high-frequency signal transmission by insertion loss test.

ACKNOWLEDGEMENT

26 
 
 This work is supported by Guangdong Innovative Research Team Program

(NO.201301C0105324342), the Open Foundation of State Key Laboratory of Electronic Thin Films

and Integrated Devices (KFJJ201509) and Guangdong Application Technology Program

(2015B010127012).

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29 
 
 30 
 
CAPTIONS:
Fig. 1. Schematic diagrams illustrating the process of NEAP on copper foil surface.

Fig. 2. Signal loss test structure fabricated by Panasonic M6 substrate

Fig. 3. (a) SEM surface morphology of copper foil by NEAP; (b) SEM surface morphology of

copper foil by brown oxidation; (c) 3D microscope morphology of copper foil by NEAP; (d) 3D

microscope morphology of copper foil by brown oxidation

Fig. 4. Signal loss measurement of NEAP and Brown Oxide treatment

Fig. 5. SEM images of copper surface morphologies at varied immersion times: (a) 0 s, (b) 40 s, (c)

80 s, and (d) 120 s

Fig. 6. The thickness (a) and the peel strength (b) of tin layer varied with immersion time(c)

lamination adhesion comparison of different surface treatments.

Fig. 7. Optical(a) and SEM(b) image of the peeled interface

Fig. 8. The X-ray photoelectron spectroscopy (XPS) results of the PI part(a) and the metal part(b) ((c)

C1s spectra, (d)O 1s spectra)

Fig. 9. (a) Graizing incidence X-ray diffraction patterns of copper foils after oxidation in NEAP

process (b) XPS about the content of O on the surface after different immersion time

31 
 
Fig. 1
 
 
 
 
 

32 
 
Fig. 2
 
 
 
 
 

33 
 
Fig. 3

 
 
 
 
 

34 
 
Fig. 4
 
 
 
 
0
NEAP
Brown Oxide
-15
Signal Loss(dB/m)

-30

-45

-60

-75
0 5 10 15 20
Frequency(GHz)

35 
 
Fig. 5
 
 
 
 
 

 
 
 
 
 

36 
 
Fig. 6

(a)
0.4
(b) 0.9
0.3 0.8

Peel Strength(N/mm)
Tin Thickness(μm)

0.2 0.7

0.6
0.1

0.5

0.0

0 80 160 240 320 400 0 100 200 300 400

Immersion time(s) Immersion time (s)

(c) 1.0
0.8
Peel Strength(N/mm)

0.6

0.4

0.2

0.0
NEAP Brown Oxide Copper

37 
 
Fig. 7

38 
 
Fig. 8

(a) Atomic %
O1s (b) Atomic %
O1s
C1s
C1s C1s 70.99
C1s 69.97
O1s 22.9 O1s 22.94
N1s 3.05 N1s 3.08
Si2s 4.08 Si2s 3

Intensity
Intensity

N1s
N1s

800 600 400 200 0 800 600 400 200 0

Binding Energy(eV) Binding Energy(eV)

(c) C1s spectra in PI

Part After Peeled (d) O1s Spectra in PI
Part After Peeled
C1s spectra in the
O1s Spectra in the
Metal Part After Peeled
Metal Part After Peeled
Intensity

Intensity

292 288 284 280 27

540 536 532 528 524
Binding Energy(eV) Binding Energy(eV)

39 
 
Fig. 9

(a)  snxOy (b) 39.38%

40s
120s
CuxSny 400s
35.36%
Intensity(Counts)

31.86%

Intensity
 


 

20 40 60 80 525 530 535 540 545

2(degree) Binding Energy(eV)

4