LOW TEMPERATURE CURABLE SCREEN PRINTABLE

SILVER PASTES

Seminar Report

MM396

Submitted in partial fulfillment of the requirements for the award of the degree of

Bachelor of Technology
in
Metallurgical Engineering and Materials Science

By

Ramzan Crescent Noushad (Roll No.: 200110087)

Department of Metallurgical Engineering and Materials Science

Indian Institute of Technology Bombay

Mumbai 400076

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 CERTIFICATE

This seminar report titled “Low temperature curable screen printable silver pastes” by Ramzan
Crescent Noushad (200110087) is approved for the course MM396.

Examiners

Supervisor

Date: 01/04/2024

2
 DECLARATION

I declare that this written report submission titled "Low temperature curable screen printable
silver pastes" contains my own words, and that I have adequately credited and referenced the
original sources when others' ideas or words have been incorporated. I further declare that I have
followed all academic honesty and integrity rules in my submission and have not misrepresented
or faked any idea, data, fact, or source. I understand that any violation of the foregoing will
result in disciplinary action by the institute, as well as legal action from the
sources who were not correctly referenced or from whose sufficient permission was not obtained
when required.

Date: 01/04/2024 Ramzan Crescent Noushad

(200110087)

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 ACKNOWLEDGEMENT

I would like to express my gratitude to Prof. Parag Bhargava, my seminar guide, for his
guidance with inputs and recommendations, as well as for presenting me with a fascinating topic
to work on.

I would also like to thank Prof. Aswani Yella and Prof. Prasanna Kumar for keeping us
informed on the seminar procedure.

Date: 01/04/2024 Ramzan Crescent Noushad

(200110087)

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 TABLE OF CONTENTS

ABSTRACT 6
1. INTRODUCTION 6
2. EFFECT OF SILVER PARTICLE SIZES ON THE RESISTIVITY OF CONDUCTIVE 6
ADHESIVES
2.1 Micro-sized and mixed sized particles 7
3. EFFECT OF CURING AGENTS 7
3.1 Resistivity of the conductive adhesives 8
3.2 Adhesion 8
3.3 Flexibility 8
4. EFFECT OF METALLO-ORGANIC DECOMPOSITION AGENTS 9
4.1 Dependence of resistivity on curing time and curing temperature 10
5. DRAWBACKS OF EPOXY RESIN AND NOVEL METHOD OF USING 11
POLYURETHANE RESIN FOR FLEXIBLE ELECTRONICS
5.1 Bulk Resistivity 11
5.2 Flexibility properties 12
REFERENCES 12

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 Low temperature curable screen printable silver pastes

Ramzan Crescent Noushad, Guided by Prof. Parag Bhargava

Abstract: Additive manufacturing of printed electronics is a growing field accompanied by increasing

demands for reliable and integrable functional flexible printed electronic devices. The screen printing
process emerges as a superior manufacturing process due to its advantages, including mass production,
device scalability, and system applicability. This article explores recent developments in low temperature
curable screen printable silver pastes, addressing key challenges in achieving high-performance printed
electronic devices. The focus is on novel formulations that allow curing at temperatures significantly
lower than conventional methods, expanding the range of compatible substrates and reducing energy
consumption during the manufacturing process. The article discusses the impact of these advancements
on the overall performance, conductivity, stability, adhesion, flexibility and printability of the silver
traces.

1. INTRODUCTION

The realm of electronic packaging involves integrating multiple components into a cohesive system both
mechanically and electrically, traditionally relying on tin/lead solders. However, concerns about the
environmental and health impacts of lead have prompted restrictions from countries like Japan and the
European Union. Consequently, significant efforts have been directed towards finding environmentally
friendly alternatives. In the realm of electrically conductive adhesives (ECAs), the most promising lead-
free options typically combine a polymer matrix and conductive fillers. These fillers are essential for
achieving the necessary electrical conductivity, while the polymer matrix serves mechanical
interconnection purposes. Various materials, including gold, silver, nickel, copper, graphite, and carbon
nanotubes, have been explored as potential fillers for ECAs.
Silver, being highly conductive and stable, is commonly favored. Despite their advantages such as eco-
friendliness and moderate operating conditions compared to lead-based solders, conventional ECAs face
challenges in achieving the required high electrical conductivity for widespread adoption. In the realm of
flexible electronics, components must meet criteria like low-temperature processing, strong adhesion to
polymer-based substrates, cost-effectiveness, speed in manufacturing, and high performance. Recently,
there has been exploration into low-curing-temperature conductor technology involving metallo-organic
decomposition (MOD) compound additions to create a three-dimensional metal network. MOD compounds
are typically synthetic metallo-organic salts that can decompose at low temperatures, resulting in the
precipitation of a metal or oxide, depending on the metal and environmental conditions.

2. EFFECT OF SILVER PARTICLE SIZES ON THE RESISTIVITY OF CONDUCTIVE

ADHESIVES

Polymers in conductive adhesives assist in binding the conductive particles to the substrates. However,
most polymers have a relatively low curing temperature, typically below 250 ℃, which isn't sufficient to
fuse the conductive metallic particles together. Consequently, a significant amount of metallic particles
may be required to ensure adequate conductivity, posing processing challenges for composite materials.
One solution to this issue involves using particles with a high aspect ratio, such as flakes or fibers, which
facilitate easier contact.
Interestingly, research suggests that in certain scenarios, conductivity can still be achieved even when
particles aren't directly in contact, thanks to a tunneling mechanism [1]. However, for this mechanism to
work, the distance between particles must be less than 10nm. Therefore, nano-sized silver particles could
serve as a substitute for conventional micro-sized ones. A study conducted by researchers at the National
Tsing Hua University [2] examines the impact of micro-sized, nano-sized, and mixed-sized silver particles
on the resistivity or conductivity of electrically conductive adhesives.
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2.1 Micro-sized and mixed sized particles

The experiment detailed in [2] revealed that the percolation threshold for the film occurs at approximately
11% volume fraction of silver (Ag), marked by a rapid decrease in resistivity. At a volume fraction of 15%,
the resistivity of the film is 0.01 Ωcm, which further decreases to 3 × 10−4 Ωcm at around 32% volume
fraction. The introduction of nano-sized silver particles into the system led to an increase in resistivity in
all scenarios except at the percolation threshold, where it decreased significantly. This phenomenon occurs
because near the percolation threshold, the addition of nano-sized particles aids in establishing a
conductive path, thereby reducing resistivity. Conversely, in other cases, where micro-sized silver flakes
alone were sufficient to form a conductive path, the addition of nano-sized silver colloids had a detrimental
effect due to contact resistances. While heating the film to higher temperatures can mitigate this effect, it
may pose challenges if the polymer substrate has a low curing temperature, potentially compromising
substrate integrity.

Fig 1. Resistivity of micro-sized and mixed-sized films as a function of Ag volume fractions (solid
triangle ¼ micro-sized samples; the rest mixed-sized samples; bar indicating range of measurements). [2]

3. EFFECT OF CURING AGENTS

Since epoxy resins are primarily used as a medium to bind conductive fillers to the matrix, different curing
agents work by different mechanisms helping to cure the conductive adhesives by aiding in the
crosslinking of the resins. In this section, we look at three different curing agents name dicyandiamide, p-
hydroxyphenylacetic acid, tetraethylene pentaamine and its effect on curing time and curing temperature
with reference to the work done by Xiao Qing Wang, Wei Ping Gan, Feng Xiang and Bi Yuan Li [5].
Dicyandiamide is a latent curing agent, meaning it remains inactive until triggered by heat. Upon heating
dicyandiamide decomposes, releasing ammonia and forming reactive intermediates that crosslink the
epoxy molecules, leading to curing or hardening of the resin.

From left: dicyandiamide, p-hydroxyphenylacetic acid, tetraethylene pentaamine

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During this particular experiment, all three samples were heated to a temperature of 150 ºC for different
curing times

3.1 Resistivity of the conductive adhesives

Resistivity measurements using a four-probe resistivity tester. Resistivity of all three samples becomes
constant after a long curing time. The sample prepared using tetraethylene pentaamine has no resistivity
change for curing times 40 min, 60 min and higher and has the least resistivity among all three samples.
This shows that tetraethylene pentaamine is the best curing agent [5] with respect to providing the best
conductivity as it can make a greater shrinkage and form a denser electrically conductive network than the
other two types of curing agents

Fig 2. Resistivity with respect to curing time in minute of samples printed on a PET film, 1#
dicyandiamide, 2# p-hydroxyphenylacetic acid, 3# tetraethylene pentaamine [5]

3.2 Adhesion

Adhesion plays a critical role in ensuring the long-term performance and reliability of electronic devices.
Electrically conductive adhesives (ECAs) with stable adhesion properties maintain both their electrical
conductivity and mechanical integrity throughout the operational lifespan of the device, thereby ensuring
consistent performance and minimizing the need for maintenance or repairs. To assess adhesion, samples
undergo a process where multiple scratches (in cross grids) are made in various positions. A transparent
adhesive tape is then applied and subsequently peeled off from the adhesive sample, allowing measurement
of the detachment area. A smaller detachment area indicates better adhesion. All three cured adhesives
exhibited a detachment area of less than 5%, indicating strong adhesion. [5].

Fig 3. Schematic diagram of adhesion level 1 through 4 from a) to d) [5]

3.3 Flexibilty

Flexible electrically conductive adhesives (ECAs) facilitate the development of electronics featuring
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bendable or stretchable components, which is especially crucial in wearable technology, flexible displays,
and other emerging fields where conventional rigid bonding methods are unsuitable. The flexibility of
these adhesives is assessed by bending the samples to the left and right and allowing them to return to their
original position. After multiple bending cycles, it's observed that the resistivity of the samples increases
due to surface damage caused by the silver flakes. However, some samples exhibit better performance than
others. Specifically, the dicyandiamide sample shows a 51% increase in resistivity, the p-
hydroxyphenylacetic acid sample experiences a 90% increase, while the tetraethylenepentamine sample
only sees a 28% increase. These results, observed after 32 bending cycles, suggest that
tetraethylenepentamine serves as a superior curing agent, forming a stronger conductive network that is
more resistant to bending. This makes it particularly well-suited for applications in flexible electronics.
Tetraethylenepentamine possesses a higher number of active hydrogen equivalents compared to the other
two curing agents [5]. This characteristic enables it to more readily form bonds with molecular chains,
particularly binding to epoxy groups at lower curing temperatures. As a result, utilizing
tetraethylenepentamine as a curing agent allows for the curing of silver conductive adhesive at lower
temperatures, thereby enhancing flexibility. Additionally, the lower curing temperature reduces the damage
typically associated with the curing process compared to higher temperatures.

4. EFFECT OF METALLO-ORGANIC DECOMPOSITION AGENTS

The main disadvantage of using silver as a filler in an electrically conductive adhesive is its high melting
point. Since we are using a polymer resin which provides the desired mechanical properties, these are
bound to degrade at higher temperatures. One solution proposed to this problem is to use silver
nanoparticles as discussed above. The silver nanoparticles have lower melting points than its bulk
counterparts and hence the curing process can be done at a lower temperature. But this raises the issue of
quantum tunneling as discussed in section 2. Therefore, another method proposed to deposit silver at lower
temperatures is to use silver metalloorganic compounds like silver neodecanoate with the addition of silver
flake to immobilize the compounds during melting and decomposition. The MOD-metal flake mixture
retains its structure when heated and transforms into a tightly bonded, clearly defined conductor at
temperatures compatible with polymer-based circuit board substrates. Its electrical conductivity matches
that achieved by conventional thick-film conductors sintered at high temperatures exceeding 700°C. The
metalloorganic compounds are synthetic and decompose at low temperatures to precipitate the metal or
metal oxide depending on the metal and the atmosphere.
With reference to the study published by Chun-An Lu [6], they experimented with six different
metalloorganic compounds and their impact on resistivity and decomposition temperatures. The
metalloorganic compounds used were silver 2-ethylhexanoate, silver oxalate, silver stearate, silver
cyclohexylbutyrate and behemic acid silver salt. Their chemical formula, molecular weight and chemical
structure are given in Table 1

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 Table 1. Information on MOD chemicals [6]

4.1 Dependence of resistivity on curing time and curing temperature

The variation of resistivity of all metallorganic-silver flake pastes along with resistivity of paste made from
pure silver flakes with curing time at a temperature of 200 °C and 300 °C are given in figure 4

Fig 4. Resistivity of silver films with additions of various MOD agents cured for various times at (a) 250
and (b) 300C. [6]

We can see from both the graphs that silver flakes enhanced with metalloorganic compounds such as silver
oxalate and silver stearate perform better at lower curing temperatures of 250 °C although pure silver
flakes perform better at higher temperatures [6]. Hence it confirms the idea that metalloorganic compounds
decompose to form metallic silver that can greatly enhance the conductive network between silver flakes at
lower temperatures

A similar graph on variation of resistivity with curing temperature at curing times of 5 minutes and 10
minutes are given in figure 5

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 Fig 5. Resistivity of silver films with additions of various MOD agents cured at various temperatures for
(a) 5min and (b) 10min. [6]

Again, even though at 10 minutes pure silver flakes perform better, at lower curing times silver flakes
enhanced with metalloorganic compounds like silver oxalate and silver stearate perform better. Since in the
industry, we require lower curing times and curing temperatures for efficient manufacturing addition of
silver organo-metallic compounds can greatly enhance the properties of silver pastes for electrically
conductive adhesives. Silver 2-ethylhexanoate stands out among different MOD agents due to its notably
low decomposition temperature of 190.3°C. This compound facilitates the formation of metallic silver
particles, which effectively connect the silver flake powders, leading to a reduction in resistivity even at
relatively low temperatures, as low as 200° [6].

5. DRAWBACKS OF EPOXY RESIN AND NOVEL METHOD OF USING POLYURETHANE

RESIN FOR FLEXIBLE ELECTRONICS

Conventional epoxy-based electrically conductive adhesives (ECAs) are hindered by their inflexibility,
whereas silicone-based ECAs often exhibit restricted conductivity, typically with resistivity exceeding
2.0 × 10−4 Ω cm. The work done by Zhou Li and colleagues [4] present a new solution that makes the
electrically conductive adhesives have low curing temperature, great mechanical properties, adhesion
strength and excellent electrical conductivity. They developed polyurethane based flexible ECA that has all
the above properties.

5.1 Bulk Resistivity

Achieving high electrical conductivities typically involves incorporating silver nanoparticles [3] or silver
nanoparticle-decorated carbon nanotubes (CNTs), [28,29] as these nanoparticles can be sintered at
relatively low temperatures (approximately 250°C or below), effectively reducing contact resistance [3].
However, the dispersion of metallic nanoparticles within the polymer matrix presents significant
challenges, compounded by the ongoing high cost of nanoparticles. In contrast, PU-ECA offers a simpler
route to achieving ultrahigh electrical conductivity by optimizing the PU resin formulation, bypassing the
need for expensive nanoparticles or complex preparation methods. The exceptional conductivity of PU-
ECA can be attributed to the substantial shrinkage during PU-ECA curing results in an increased volume
percentage of silver post-curing.

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 Fig 6. Bulk resistivity of PU-ECA cured at different temperatures as compared with other interconnect
materials for flexible electronics. [3]

5.2 Flexibility properties

The polyurethane based electrically conductive adhesive was subjected to different types of deformation
tests like three-point bending test. The results show that the resistance stays the same even after 100 cycles
of bending and the change in resistance is below 10% when bending at flexural strains over 4% [3]. The
necking between adjacent silver particles and their rough surfaces as a result of the PEG treatment can be a
cause for this. PEG (polyethlylene glycol) is used as a curing agent that substantially decreases the contact
resistance and reduces silver carboxylate to form silver nanoparticles at low curing temperatures of 150 C.

REFERENCES

1. Ruschau GR, Yoshikawa S, Newnham RE. Resistivities of conductive composites, Journal of

Applied Physics, (1992) 72:953
2. Hsien-Hsuen Leea, Kan-Sen Choua, Zong-Whie Shih, Effect of nano-sized silver particles on the
resistivity of polymeric conductive adhesives, International Journal of Adhesion & Adhesives 25
(2005) 437–441
3. Highly Conductive, Flexible, Polyurethane-Based Adhesives for Flexible and Printed Electronics Zhuo
Li, Rongwei Zhang, Kyoung-Sik Moon, Yan Liu, Kristen Hansen, Taoran Le, and C. P. Wong
4. Fabrication of high performance printed flexible conductors by doping of polyaniline nanomaterials into
silver paste Jiayue Wen,a Yanhong Tian, J.Mater. Chem. C,2019, 7, 1188
5. Effect of curing agent and curing substrate on low temperature curable silver conductive adhesive
Xiao-Qing Wang · Wei-Ping Gan1 · Feng Xiang1 · Bi-Yuan Li. Journal of Materials Science: Materials
in Electronics (2019) 30:2829–2836
6. Effects of Metallo-Organic Decomposition Agents on Thermal Decomposition and Electrical
Conductivity of Low-Temperature-Curing Silver Paste. Chun-An Lu et al 2006 Jpn. J. Appl. Phys. 45
6987
7. Low cost and highly conductive elastic composites for flexible and printable electronics. Yougen Hu,
Tao Zhao,Pengli Zhu, J.Mater. Chem. C,2016, 4,5839
8. Screen printing: a technology for the batch fabrication of integrated chemical-sensor arrays Howard D.
Goldberg, Richard B. Brown. Sensors and Actuators B 21 (1994) 171-183
9. Synthesis Of Silver Flakes And Their Application As Conductive Filler For Low-Curing-Temperature
Silver Pastes Haijiao Zhan, Jiayu Guo, Jiali Shen, Xiaorong Wang, Zhonghua Fan, Bing Guo, Wei Liu,1
And Hangyan Shen, Journal of ELECTRONIC MATERIALS, Vol. 48, No. 5, 2019
10. Ultra-low temperature curable nano-silver conductive adhesive for piezoelectric composite material
Chao Yana, Qingwei Liaoa, Xingli Zhou, Likun Wang, Chao Zhong, Di Zhang

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