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Solar Cell Metallization by Laser Transfer of Metal Micro-droplets

Article in Energy Procedia · April 2015

DOI: 10.1016/j.egypro.2015.03.298

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Energy Procedia 67 (2015) 147 – 155

5th Workshop on Metallization for Crystalline Silicon Solar Cells

Solar cell metallization by laser transfer of metal micro-droplets

Michael Zenoua,b*, Lee Baronb, Amir Sa'arb and Zvi Kotlera
a
Orbotech Ltd, P.O. Box 215, Yavne 81101, Israel.
b
Racah Institute of Physics and the Harvey M. Kruger Center for Nanoscience & Nanotechnology, the Hebrew University of Jerusalem,,
Jerusalem 91904, Israel

Abstract

Laser Induced Forward Transfer (LIFT) enables a non-contact, mask-less and high-resolution/high-aspect ratio printing of
various metals. However, the small gap between the donor (print head) and the acceptor (silicon wafer), which is typically
<25 µm, limits its wider use in manufacturing. We demonstrate LIFT printing of metal micro-droplets from a gap larger than
100 μm to provide high quality electrical contacts to silicon. Post annealing process is not required as the contacts are formed
instantaneously during the LIFT process. Printing aluminum contacts on p-type (resistivity of 10-30 Ÿ·cm) and p+ type
(0.01 Ÿ·cm) Si substrates yields a specific contact resistance of 0.15 mŸ·cm2 and 0.03 mŸ·cm2 respectively. Finally, we
demonstrate the use of LIFT metallization for serially connecting few vertical solar cells that are locally isolated by porous
silicon.

© 2015 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
© 2015 The Authors. Published by Elsevier Ltd.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of Gunnar Schubert, Guy Beaucarne and Jaap Hoornstra.
Peer-review under the responsibility of Gunnar Schubert, Guy Beaucarne and Jaap Hoornstra
Keywords: laser priting , solar cell metallizaion, high volatge solar cells, vertical solar cell

1. Introduction

The solar photovoltaic (PV) industry routinely uses the screen printing technology for cell metallization utilizing
metal micro particles pastes to create electrical contacts [1-3]. This technology is reliable and cost effective and
therefore, allows mass production of solar cells. Still, this metallization approach is known to be the main reason for
efficiency losses. Compared to an ideal solar cell metalized by standard vacuum process and an efficiency exceeding
24% [4], the lower cost screen printing process is characterized by a typical efficiency of ~ >19% (for Cz Si) due to

* Corresponding author. Tel.: +972-8-9423551; fax: +972-8-9423250.

E-mail address: micha-z@orbotech.com

1876-6102 © 2015 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under the responsibility of Gunnar Schubert, Guy Beaucarne and Jaap Hoornstra
doi:10.1016/j.egypro.2015.03.298
148 Michael Zenou et al. / Energy Procedia 67 (2015) 147 – 155

contact quality and larger shadowing. For example, typical width of conduction lines created by the screen printing
technique is ~60 Ɋ݉ and the aspect ratio is about 1:5 [5]. Such geometry blocks ~6% of the cell surface. High
resolution screen printing was recently demonstrated, however, it involves considerable increase in processing costs
(more complex screen, higher system maintenance and complex printing recipe) [6]. Metal paste formulations also
affect the printed line contact quality [7]. Currently, front side metallization of p-type solar cells is limited to silver
pastes, which apart from the higher cost also has a lower effective electrical contact quality compared to metal-
silicide contacts (such as silver, aluminum or copper). Replacement of silver pastes by a cheaper conductor, e.g.,
copper or aluminum, can reduce the production costs considerably, yet at present there is no printing technology
available for these metals. Screen printing also involves direct contact with the wafer and thereby limits the use of
thinner wafers to avoid breakage during the printing step [8, 9].
Alternative mask-less metallization techniques such as inkjet [8], aerosol [9], dispensing [10] and laser micro-
sintering [11] were proposed recently. Yet, these techniques use complex silver formulations and therefore, are
inferior to screen printing. Chemical plating of copper and nickel is another possible approach for solar cell
metallization [12], however it involves a complementary process to define the seed layer [13]. A promising method
(Fig 1.a) uses Laser Induced forward transfer (LIFT) to deposit a seed layer and was shown recently to provide
direct contact through the passivation layer [14-15]. Still, the very narrow gap between donor (print head) and
acceptor (Silicon wafer), typically < 25 µm (in some cases full contact is required), makes the industrial realization
quite challenging.
Transfer of molten micro-droplets using LIFT was demonstrated several years ago [16] and later also sub-micron
droplets transfer was revealed using femto-second lasers [17]. Molten metal droplet jetting can be obtained under
specific conditions of laser pulse width, energy and the metal layer. The transfer mechanism consists of a complex
hydrodynamic process involving a liquid near a free surface [18, 19]. One important advantage here has to do with
jetting much smaller droplets [16, 17], smaller than the spot size. Still there is a strict requirement to jet from a small
gap distance to guarantee reasonable print quality. There is another, novel, printing regime [20] with which it is
possible to overcome such a limitation and go beyond 100 μm gap with rather good printing quality and accuracy.
This is made possible by using a temporal pulse regime that induces thermal formation of a quasi-nozzle within the
jetting process itself, which helps guide the jetting.
In this work we demonstrate mainly LIFT printed aluminum micro-droplets on a p-type silicon wafer and
investigate the electrical properties of the contact. We have found that the LIFT printing method allows direct
formation of ohmic contacts to the wafer without the need for further complex annealing processes. Moreover, it
turns out that it is possible to practically tune the contact characteristics from Schottky-like to ohmic-like by
controlling the laser pulse energy used for LIFT jetting. Finally, we show that this metallization process can be
exploited for high voltage solar cells [21-24].

2. Experimental

2.1. Laser setup

The laser source is a passive Q-switch laser emitting at 532 nm from Teem Photonics (model ‘Power Chip’). The
pulse width is 400 pico-seconds and maximal pulse energy Ep=30 µJ. Laser power is controlled by an acousto-optics
modulator (‘Crystal Technology’). A fast scanning mirror serves for scanning the laser beam in the field of view of
the objective with a suitable relay optics which keeps the chief ray in the same position at the entrance pupil of the
objective for all incidence angles. Such a configuration allows in-situ imaging of the laser process using a single
objective for both imaging and processing. A zoom-beam-expander serves for tuning the spot size (4σ) from
d=4 μm to 32 μm (using x10 objective). The Donor and the Receiver holder are both controlled by XYZ motorized
stages. A distance meter with a resolution of 1 μm is used to determine the exact gap between the donor and receiver
during the printing process.
 Michael Zenou et al. / Energy Procedia 67 (2015) 147 – 155 149

2.2. Contact characteristics

To evaluate the contact characteristics (either ohmic or Schottky-type), two types of mono-crystalline Si wafers
were used, a p-type with resistivity of 10-30 Ÿ·cm and a p+-type with resistivity of 0.01 Ÿ·cm. The backside contact
was made of a thermally evaporated aluminum layer, later annealed at 470°C for 30 minutes. Such a contact layer
typically provides ohmic contact with specific contact resistance >10-2 mŸ·cm2 for both wafer types. On the front
side we prepare a reference pad by thermal evaporation followed by photo-lithography using direct write laser
patterning. The wafers were kept in oxygen-free conditions to avoid passivation layer formation up until the LIFT
printing experiment takes place in open air environment. We LIFT printed several rectangular aluminum pads,
150x650 μm2 each, employing different pulse energies, and then measured the IV curves between the rear contact
and the front face pads with a source meter (model 4200, Keithley). We made the same measurements with the
evaporated reference pad before and after annealing.

Fig. 1. A scheme of the method used to evaluate the contact characteristics.

2.3. Specific contact resistivity

For a quantitative evaluation of the specific contact resistance we have used a modified version of transmission
line measurement (TLM) [25]. Usually the TLM relies on a thin emitter layer so one can neglect the current
penetration profile and assume a linear dependence of the resistance on the distance between pads. In our case
though, and in order to facilitate the experiment, we have used the test wafers described earlier (section 2.2) and
printed a TLM structure which consists of an array of rectangular pads 150x650 μm2 each, at distances 300, 600 and
1200 μm apart. Note that in this case linear dependence on distance can no longer be assumed. The resistance at
zero distance still equals two times the contact resistance of the pad. In order to extract the specific resistivity from
the measured contact resistance we approximate the effective sheet resistance of the wafer by fitting locally the
curve slope near the zero distance point. This approximation gives somewhat higher resistivity values, and therefore
the values reported in this work should be considered as “less than” rather than “equal to”.

2.4. Metallization of vertical solar cell configuration

We choose to demonstrate the special advantages of LIFT metal printing in metallization of micron-size vertical
cells separated by an insulating layer [21-24]. The cell (see Fig. 2), a high power solar cell integrated on a chip, was
developed by Tower Jazz Semiconductor [23]. The cell was prepared from a heavily doped p-type crystalline silicon
wafer, on top of which a lightly doped, p-type crystalline silicon epitaxial layer (4 μm thick) was grown. Next, using
ion implantation, p+ and n+ regions were defined. A protective layer of silicon nitride (SiN) was deposited on top by
low pressure chemical vapour deposition (LPCVD) and using deep reactive ion etching via a mask, trenches 2 μm
150 Michael Zenou et al. / Energy Procedia 67 (2015) 147 – 155

wide and 4 μm deep were etched. Metallization of these cells requires high horizontal resolution (better than 10 μm)
since the contact areas in both the n+ and p+ regions are only 10x5 μm2. This specific application while challenging
in terms of print resolution allows us to test the LIFT concept for Si metallization in full breath.

Fig. 2. (a) An SEM image of the high voltage solar cells; (b) Schematic of two cells design (cross-section view).

3. Results and Discussion

3.1. Printing properties

In order to demonstrate printing properties of metal structures by LIFT, we explore next the role of the gap size.
We use two aluminum donors with thickness h=300 nm and 500 nm. For the thinner donor (300 nm thick) the
regime is that of melt pool droplet jetting [15-18] while for the thicker the more stable LIFT regime [19-20] holds.
Square shaped metal slabs of dimension L=150 μm were printed from two gap sizes, 30 μm and 300 μm. Each slab
is made up from 100 layers, each with 6x6=36 droplets, a total of 3600 droplets (droplet overlap of 50%). We use a
3D optical microscope (Contour GT-InMotion from Bruker) to measure the 3D profile of the printed slabs.
 Michael Zenou et al. / Energy Procedia 67 (2015) 147 – 155 151

Fig. 3. Profile of LIFT printed square slabs 150 μm wide printed from a gap of 30 μm and 300 μm. (a) Al layer thickness. h=300 nm; (b)
h=500 nm.

Fig. 3 depicts average profiles of printed slabs for the two donors. Note the much better printing stability under
the enhanced LIFT conditions as compared with the melt pool case obtained for the thinner donor. A spreading
angle <0.1 mrad is obtained for the thicker donor, in contrast to 10 mrad obtained with the thinner donor. Another
observation concerns the droplet volume found to be 19 μm3 on average for h=300 nm and 32 μm3 for h=500 nm.
One can see that printing is more effective under these novel LIFT conditions in building high aspect ratio lines
needed for solar cell metallization.

3.2. Contact characteristic

Fig. 4 depicts measurements of the contact characteristics as obtained by the method described in section 2.2. The
IV curves represent results obtained for printed pads using the enhanced LIFT regime at different laser pulse
energies. The lower pulse energy was close to threshold and the higher to the spreading regime which corresponds
to multiple micro-droplets jetting. We find that at lower pulse energy the contact is of Schottky characteristic and
when the energy is increased the contact is ohmic. This is explained by the fact that at higher pulse energy the
droplets are of a larger volume and also of higher temperature. The cooling time and the silicon/droplet interface
temperature increase for higher pulse energy. It is worth noting that such a dependence is potentially of interest in
printed micro-electronics device applications, namely the capability to tune the contact characteristics from Schottky
diode to ohmic. The black lines in Fig. 5 show the contact characteristics for the thermally evaporated aluminum
pads, before and after annealing, full line and dotted line respectively. The annealed pad specific contact is in order
of 10-3 mŸ·cm2 while the printed contact with maximal energy is somewhat higher.
152 Michael Zenou et al. / Energy Procedia 67 (2015) 147 – 155

Fig. 4. IV curves for printed metal contacts at different pulse energies and references, evaporated and annealed aluminum pads.

3.3. Contact characteristic

To evaluate the specific contact resistance we have used the method describe in the section 2.3. The results are
shown in Fig. 5 where we depict results only for pulse energy values that provided ohmic contacts. We can see
relatively good specific contact resistance for the solar cell industry; all cases were below 5x10-4 mŸ·cm2. We see
no special trend as a function of energy in the case of p+-type wafer, which is due to insufficient sensitivity and
accuracy of the modified TLM method. These results are limited to silicon with no passivation layer on top. Clearly
we need next to evaluate the contact formation properties when printing on the SiN layer as done in previous work
[13, 14].We expect comparable results due to the fact that the novel LIFT regime droplets have a higher heat inertia.
 Michael Zenou et al. / Energy Procedia 67 (2015) 147 – 155 153

Fig. 5. Specific contact resistance vs. the pulse energy for p- and p+-type wafer.

3.4. Metallization of vertical solar cell

The metallization pattern of the solar cell described in section 2.4 is shown in Fig. 6. The design requires
connecting five columns of cells in parallel and the two rows in series. The metal printing part includes three
external connection pads 100 μm long for series connection of the diodes and four lines 9 μm wide for series
connection of the diodes. This pattern also demonstrates the high resolution and accuracy achievable with such a
printing method. Moreover, it also allows printing of bridges over trenches, provided they are smaller than the
droplet size (~5 μm in diameter).

Fig. 6. SEM picture of the PV cells: (a) before and (b) after metallization.
154 Michael Zenou et al. / Energy Procedia 67 (2015) 147 – 155

To characterize cell efficiency, we have used standard test conditions for photovoltaic measurements using a
Newport system composed of an Oriel IV test station and Oriel Sol3A simulator. IV curves were obtained by
applying an external bias to the cell and measuring the generated photocurrent using a Keithley model 4200 digital
source meter. Fig. 7 shows the photovoltaic effect for one and two rows of diodes. The open circuit voltage
properties show that the metallization step does not affect the circuit properties. The efficiency obtained for these
cells was 6.7% for one row of diodes and 6.2% for two rows of diodes. This is comparable to high voltage cells with
metallization carried out by standard vacuum deposition methods which report an efficiency of 7% [26].

Fig. 7. IV curve of the high voltage cells in dark and STC.

4. Conclusion

The metallization method presented in this work has a great potential to replace common PV metallization
methods like screen printing of metal pastes. We demonstrate the capability to print pure metal from the solid phase
which allows printing of a large range of metal types, such as Ti, Ni, Cu and Al which are needed for better contact
quality. This metal printing method has several other advantages: It is a non-contact method allowing safe
metallization of thinner wafers; it is a mask-less method, therefore can provide better yield and maintenance; the
high lateral resolution improves on shadowing effect; and finally direct formation of contacts, without the need for
annealing, reduces the process tact time and avoids thermal cycling. However, in order to mature this method one
needs to evaluate the contact formation and properties when printing on top of the passivation layer and to develop a
similar method to the one reported here for front size metallization.

Acknowledgements

This joint research was supported by the SES (solar energy solutions) consortium under the MAGNET program
of the chief scientist (the Israeli Ministry of Industry and Trade). We like to thank Towerjazz semiconductor [23] for
 Michael Zenou et al. / Energy Procedia 67 (2015) 147 – 155 155

providing the vertical solar cells and Inna Lyubina, for the preparation of the test samples and for her professional
advices.

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