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Microwave Flash Sintering of Inkjet-Printed Silver Tracks on Polymer Substrates
By
Jolke Perelaer, Mark Klokkenburg, Chris E. Hendriks,
and
Ulrich S. Schubert*
Within the last few decades inkjet printing has grown into amature noncontact patterning method, since it can producelarge-area patterns with high resolution at relatively high speedswhile using only small amounts of functional materials.
[1–3]
Themain fields of interest where inkjet printing can be appliedinclude the manufacturing of radiofrequency identification(RFID) tags,
[4–6]
organic thin-film transistors (OTFTs),
[7–9]
andelectrochromic devices (ECDs),
[10,11]
and are focused on thefuture of plastic electronics.
[12]
In view of these applications on polymer foils, micrometer-sized conductive features on flexible substrates are essential. Tofabricate conductive features onto polymer substrates, solution-processable materials are often used. The most frequently usedare dispersions of silver nanoparticles in an organic solvent.
[13–15]
Inks of silver nanoparticle dispersions are relatively easy toprepare and, moreover, silver has the lowest resistivity of allmetals (1.59
mV
Á
cm). After printing and evaporation of thesolvent, the particles require a thermal-processing step to renderthe features conductive by removing the organic binder that ispresentaround the nanoparticles. Innonpolar solvents,long alkylchainswithapolarhead,likethiolsorcarboxylicacids,areusually used to stabilize the nanoparticles.
[16,17]
Steric stabilization of these particles in nonpolar solvents substantially screens van derWaals attractions and introduces steep steric repulsion betweenthe particles at contact, which avoids agglomeration.
[18]
Inaddition, organic binders are often added to the ink to assure not only mechanical integrity and adhesion to the substrate, but alsoto promote the printability of the ink.
[16]
Nanoparticleswithadiameterbelow50nmhave asignificantly reduced sintering temperature, typically between 160 and 300
8
C,which is well below the melting temperature of the bulk material(
T 
m
¼
963
8
C).
[19,20]
Despite these low sintering temperaturesconventional heating methods are still not compatible withcommon polymer foils, such as polycarbonate (PC) andpolyethylene terephthalate (PET), due to their low glass-transitiontemperatures (
T 
g
). In fact, only the expensive high-performancepolymers, like polytetrafluoroethylene (PTFE), poly(ether etherketone) (PEEK), and polyimide (PI) can be used at thesetemperatures. This represents, however, a significant drawback for the implementation in a large-area production of plasticelectronics, being unfavorable in terms of costs. Furthermore,thelongsinteringtime of60minormorethatis generallyrequired tocreate conductive features also obstructs industrial implementa-tion. Therefore, other techniques have to be used in order tofacilitate fast and selective heating of materials.One selective technique for nanoparticle sintering that hasbeen described in literature is based on an argon-ion laser beamthat follows the as-printed feature and selectively sinters thecentral region. Features with a line width smaller than 10
m
mhave been created with this technique.
[21]
However, the largeoverallthermal energyimpacttogether withthe lowwritingspeedof 0.2mm s
À
1
of the translational stage are limiting factors.
[22]
A faster alternative to selectively heat silver nanoparticles is touse microwave radiation.
[23]
Ceramics and other dielectricmaterials can be heated by microwaves due to dielectric lossesthat are caused by dipole polarization. Under ambient conditions,however, metals behave as reflectors for microwave radiation,because oftheir small skindepth,which is definedasthe distanceat which the incident power is reduced to half of its initialvalue.
[24]
The small skin depth results from the high conductance
s 
and the high dielectric loss factor
e
00
together with a smallcapacitance. When instead of bulk material, the metal consists of particles and/or is heated to at least 400
8
C, the materials absorbsmicrowave radiation to a greater extent.
[25,26]
It is believed thattheconductive particle interaction with microwave radiation, i.e.,inductive coupling, is mainly based on Maxwell–Wagnerpolarization, which results from the accumulation of charge at the materials interfaces, electric conduction, and eddy cur-rents.
[25]
However, the main reasons for successful heating of metallic particles through microwave radiation are not yet fully understood.In contrast to the relatively strong microwave absorption by theconductive particles, the polarization of dipoles in thermoplasticpolymers below the
T 
g
is limited, which makes the polymer foil’sskin depth almost infinite, hence transparent, to microwaveradiation. Therefore, only the conductive particles absorb themicrowaves and can be sintered selectively. Recently, it has beenshownthatitispossibletocreateconductiveprintedfeatureswithmicrowave radiation within 3–4min.
[23]
The resulting conductiv-ity, however, is only approximately 5% of the bulk silver value.In this contribution, we present a study on antenna-supportedmicrowave sintering of conducted features on polymer foils. We
 C  OMM UNI   C AT I   ON
www.advmat.de
[
*
] Prof. U. S. Schubert, Dr. J. Perelaer, C. E. HendriksLaboratory of Macromolecular Chemistry and NanoscienceEindhoven University of Technology and Dutch Polymer Institute (DPI)PO Box 513, 5600 MB Eindhoven (The Netherlands)E-mail: u.s.schubert@tue.nlDr. M. KlokkenburgHolst Centre, High Tech Campus 31, 5656 AE EindhovenThe NetherlandsProf. U. S. SchubertLaboratory of Organic and Macromolecular ChemistryFriedrich-Schiller-University JenaHumboldtstr. 10, 07743 Jena (Germany)
DOI: 10.1002/adma.200901081
 Adv. Mater.
2009
,
21,
1–5
ß
2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1
Final page numbers not assigned
 
    C    O    M    M    U    N    I    C    A    T    I    O    N
www.advmat.de
inkjet printed antenna structures using a colloidal dispersion of silver nanoparticles onto a flexible polyethylene naphthalate(PEN) foil (see Fig. 1a for the template). The template consists of four metal areas, each having a surface area of 11 mm
2
.Subsequently, curing of the antenna structures was performed at 110
8
C for 60min.These antennae wereusedboth tomeasuretheresistance of the single ink line and to capture electromagneticwaves. After this, a single silver ink line was printed over themetallicprobes(blacklineinFig.1a)andquicklycuredinanovenfor 1–5min at a temperature of 110
8
C. This relatively short timewas chosen to stimulate solvent evaporation, but to minimizethermal curing. After this treatment, the single line had arelatively high resistance in the order of 10
2
to 10
4
V
. The samplewas subsequently exposed to microwave radiation for at least 1 s,while applying the lowest set-power of 1W. This resulted in apronounceddecreaseoftheresistanceofwhichtheexactoutcomedepends on the initial resistance.The
antenna effect 
, which reflects the capability to absorbmicrowaves into the material, was studied systematically by altering the surface area of the electrodes of the template. Whenincreasing the size of the electrodes a rapid decrease of theresistance after microwave exposure was revealed, as is shown inFigure 1b and c for pre-dried samples. This may be explained by the improved absorption of the microwaves due to an increasedsurface area of the electrodes.The
antenna effect 
, however, is larger when the initial lineresistance is small (Fig. 1b), which is likely due to enhanced heat conduction from the electrodes to the ink line. For ink lines withan initially large resistance (Fig. 1c), the energy transfer is stillvery effective, although the total antenna area has less impact onthe final resistance. The data obtained in the absence of antennas(
A 
¼
0 mm
2
) clearly demonstrate that the energy absorption by the printed line is negligibly small. The absorption of microwaveradiation may be improved by the presence of antennae due to asubsequently smaller impedance mismatch between air andsample. According to Zuckerman et al. the intrinsic impedance
Z 
of a circuit relative to free space is given by 
Z 
¼
Z 
0
 ffiffiffiffiffi 
"
Ã
p 
(1)
where
Z 
0
is the impedance of the free space (
Z 
0
¼
377
V
) and
e
*
isthe complex permittivity of the circuit relative to free space. Thecomplex permittivity is related to the dielectric constant and lossfactor according to
"
r 
¼
"
0
þ
i 
"
00
¼
"
0
þ
i 
s v
Á
"
0
(2)
where the real part 
e
0
is the ability of the material to store energy and where the imaginarypart 
e
00
accounts forthe losses via energy dissipation.Thereflection,i.e.,impedancemismatch
Z/Z 
0
,scaleswith the square root of the complex permittivity 
e
*
and thus, inour experiments, with the resistance of the electrodes, whichdepends on their total surface area.
[27]
Figure2depictstheeffect oftheinitialresistance oftheprintedline on the final resistance after microwave exposure for different times.Whentheflashingtimeisequalto1s,theresistancecanbedecreased to a few Ohms per line, only if the initial resistance iswithin a range of 10
2
to 10
4
V
. Above a threshold if 10
5
V
, themicrowave coupling and transfer at the antenna-line interface isinsufficient to accomplish pronounced sintering of the nano-particles and to form a percolating network through the line.
Figure 1.
Schematic representation of the printed template (a) with foursilver electrodes/antennae in gray and a single silver line inkjet printed ontop of the antennae in black. The total length of the line is 1.6cm. Influenceof the total surface of the four electrodes on the template for an initial lineresistanceof100
V
(b)and1k
V
(c)onmicrowaveflashexposurefor1–60s.
2
ß
2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Mater.
2009
,
21,
1–5
Final page numbers not assigned
 
 C  OMM UNI   C AT I   ON
www.advmat.de
Therefore, longer sintering times are necessary for lowering theresistance. As shown in Figure 2, an exposure of 60s increasesthe initial threshold resistance from 10
5
V
up to 10
7
V
. Moreover,higher power settings and/or longer exposure times would evenfurther increase this threshold value.To highlight the effect of the surface area of the ink line on thefinal resistance, lines were inkjet printed onto the foil withmodified surface wetting properties, while using equal print settings to dispense the same volume of material. On the onehand, the surface wetting was decreased by increasing the platentemperature to 60
8
C, which stimulates solvent evaporation andtherefore results in a different line geometry.
[3,28]
On the otherhand, a plasma surface treatment was applied to increase thesurface energy, which improves the wetting behavior of the ink,and consequently gives broader lines. The line width wasmeasured to be 172 and 161
m
m for lines printed at roomtemperature and 60
8
C, respectively, while after plasma treatment the lines were 353
m
m in width. Figure 3 shows the effect of thelinewidthontheresistanceaftermicrowaveflashexposure.Itcanbe inferred that a narrow line shows a three times higherresistance than a broad line for sintering times shorter than 10s.This suggests that there is a positive correlation between surfacearea of the line, which is directly linked to the line width, and theamount of energy absorbed. However, this surface effect diminishes after 30s of microwave exposure. This indicates that the surface area of the electrodes mainly determines the effectivesintering time.The electrical resistivity 
r
of an inkjet printed line was thencalculated from the resistance
R 
, the length
‘
, and the crosssectional area
A 
of the line, using
r
¼
R 
Á
A 
=‘
. The maximumconductivity 1
=
r
ð Þ
for the maximum surface area (44 mm
2
) of theantennae was found to be 34% when compared to the theoreticalvalue of bulk silver. The lowest revealed conductivity was 10% forthe antennae with a surface area of 20 mm
2
. This value, however,is significantly larger than the 5% that was reported previously formicrowave sintering.
[23]
Scanning electron microscopy (SEM) images of the printedsilver tracks in Figure 4 show the morphology and particlepacking within the line before and after sintering. In Figure 4a, aclose-up of the unsintered but pre-cured track is depicted, wherethe silver nanoparticles with a typical diameter of 30–50nm canstill be distinguished individually. Upon drying, the particlesprobably have lost a part of their organic protecting shell, whichcauses the particles to form a percolating pathway for theelectrons in an early stage.
[16]
After microwave flash exposuremost of the organic material has been removed and the particles
Figure 2.
Effect of the initial line resistance (
R
before
) on the resistance aftermicrowave flash exposure (
R
after
) for 1 or 60s.
Figure 3.
Effect of the line width on the resistance per line after 1–60smicrowave flash exposure.
Figure 4.
Scanning electronmicroscopy (SEM)images of an inkjet printedsilver track on a polymer substrate before (a) and after sintering (b). Theunsintered track (a) shows a detailed view of the silver nanoparticles with atypical diameter between 30 and 50nm. A sintered track (b) after flashexposure to microwaves with a total electrode area of 20mm
2
. The insetshows a more detailed view into the track.
 Adv. Mater.
2009
,
21,
1–5
ß
2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
3
Final page numbers not assigned
of 00

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