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The improvement of solar cell efficiency in industrial Polished Czochralski p-type silicon wafers with
production has motivated important contributions to rear sur- 1.5⫾ 0.5 ⍀ cm resistivity were fully covered with a dielec-
face passivation techniques.1–3 However, the optimization of tric insulation layer deposited by the plasma-enhanced
the local contacts between screen-printed aluminum pastes chemical vapor deposition approach. The LCO 共d1兲 were
and silicon is not trivial and requires deeper understanding of achieved by screen printing an etching paste, which contains
the metal–semiconductor interaction. Indeed, a compromise phosphoric acid, a useful etchant of dielectric films.11 The
between the contact area and finger spacing is an essential etching of the dielectric was performed by heating the wafers
issue when reducing series resistance.4–6 On the other hand, in an infrared belt furnace for 4 min at 330 ° C. The dried
the local formation of a high-quality p+-doped layer 关back- etching paste was removed within a few seconds in an
surface-field 共BSF兲兴 to improve the cell performance,7–9 is ultrasonic bath filled with 0.2% potassium hydroxide diluted
still a challenge. Recently, it has been shown that the high with deionized water. A broad range of d1 was chosen be-
overlapping of aluminum on each side of the local contact tween 100– 500 m in steps of 50 m 共the real values are
opening is essential for a well-formed local BSF and the ⬇20 m broader due to the spreading of the etching paste兲.
minimization of the contact resistivity.10 Thereby, the design A state of the art 20 m thick aluminum contact was screen-
of the rear side pattern can influence the series resistance printed, fully covering the rear passivation layer and the
losses and the process of contact formation. In this letter, we opening lines. The alloy was formed after sintering the
search for the minimum contact spacing allowed for an op- samples following a standard firing furnace profile. Three
timal rear side pattern based on the interdiffusion between peak firing temperatures were applied: 750, 850, and
liquid aluminum and silicon. These results may have appli- 950 ° C. The sharp limits of the visible dark-gray regions
cations on screen-printed back-contacted and rear passivated 共d2兲 were measured by optical microscopy.
silicon solar cells. The aluminum layer was characterized by scanning elec-
Figure 1共a兲 shows the cross-section of a silicon solar tron microscopy 共SEM兲 and energy dispersive spectrometry/
cell with a passivated and locally contacted rear side, as a energy dispersive x-ray 共EDS/EDX兲. The three layers 共A, B,
model for this letter. Three variables describe the rear side C兲, as shown by Fig. 1共a兲, are as follows:10,12 the local BSF
structure—the width of the local contact openings 共LCO兲, d1; 共A, composition Si–1%Al兲; the eutectic layer or aluminum-
the maximum spread limit of diffused silicon in aluminum silicon alloy formation 共B, composition Al–12.6%Si兲; and
layer, d2; and the contact spacing, L p. Thus, 共d2 − d1兲 / 2 rep- the aluminum layer in porous state, C. For rear passivated
resents the spread of silicon in aluminum on each side of the solar cells, we redefine the aluminum layer in two regions;
LCO 共away from the contact area兲. As shown in the cross- 共1兲 the visible dark-gray region 共within d2兲 in hypereutectic
alloy 共composition ⬎Al– 12.6%Si兲 and 共2兲 the rest of the
sectional model of Fig. 1共a兲, the contact area between silicon
aluminum layer formed by solid particles of the aluminum
and aluminum is restricted to the LCO, d1. An aluminum
paste. Figure 2 shows on the y-axis the optical measurement
layer fully covers the rear surface. The local BSF forms in
of the dark-gray regions 共spread limit of silicon in aluminum,
the LCO at the rear of the device structure due to local
aluminum-silicon interaction. The microscope image of Fig.
1共b兲 shows a section of the rear side of a processed solar cell
with the same rear structure as shown by Fig. 1共a兲. The dark-
gray regions 共within d2兲, which are visible after firing in the
aluminum layer, do not represent the local BSF formation
because they are wider than the LCO 共d2 ⬎ d1兲. The under-
standing of this phenomenon motivated the development of
the present study. FIG. 1. 共Color online兲 共a兲 Rear passivated solar cell in cross section 共front
side simplified兲. d1: width of LCO. d2: spread limit of silicon in aluminum.
L p: contact spacing. A: BSF. B: Eutectic layer. C: Aluminum layer. 共b兲
a兲
Electronic mail: elias.urrejola@isc-konstanz.de. Section of the rear side of a solar cell showing dark-gray lines 共not to scale兲.
Furthermore, below too high firing temperatures 共fast cool- and is predicted as 75 m, 225 m, and 375 m for
ing兲, a high elastic stress field may occur in the melt during 750 ° C, 850 ° C, and 950 ° C, respectively. Thus, the width
the alloying.18 Due to the Kirkendall effect,19 which explains of the aluminum contact may be determined by the maxi-
that the rates at which two types of atoms diffuse are not the mum spread limit of diffused silicon in an aluminum layer.
same, the high generation of vacancies during the silicon- We suggest that the contact spacing should be equal or larger
aluminum interdiffusion may coalesce in the melt, causing than the maximum spread limit of diffused silicon in alumi-
the nucleation and formation of Kirkendall voids18 instead of num. Additionally, the void formation below the aluminum-
an eutectic layer. silicon contacts may be explained by the Kirkendall effect.
By cooling down the sample, the composition of silicon Our result may be applied to develop high-efficiency screen-
in the liquid-phase has to decrease following the liquid curve printed back-contacted and rear passivated solar cells suit-
of the binary system,22 however, only the edges of the LCO able for industry.
are still in direct contact with the aluminum layer due to the The authors gratefully acknowledge the financial support
presence of the void. By reaching the eutectic temperature, by the German Federal Ministry of Education and Research
no more silicon segregates and the whole remaining liquid under Contract No. 03SSF0335I, and Merck KGaA for the
solidifies, leaving a high concentration of silicon in alumi- kind supply of the etching paste.
num, away from the surface of contact 关shown by the two
maxima of Fig. 3共d兲兴. If the interaction between aluminum 1
D. Niinobe, H. Morikawa, S. Hiza, T. Sato, S. Matsuno, H. Fujioka, T.
and silicon takes place only within d2, where a visible dark- Katsura, T. Okamoto, S. Hamamoto, T. Ishihara, and S. Arimoto, Sol.
gray region is sharply delimited, the spread of silicon in the Energy Mater. Sol. Cells 95, 49 共2011兲.
2
D. Y. Lee, H. H. Lee, J. Y. Ahn, H. J. Park, J. H. Kim, H. J. Kwon, and J.
aluminum layer is diffusion-limited. Thereby, an exponential W. Jeong, Sol. Energy Mater. Sol. Cells 95, 26 共2011兲.
decrease with the distance from the center of the interface is 3
M. Hofmann, S. Janz, C. Schmidt, S. Kambor, D. Suwito, N. Kohn, J.
evident due to the Fick’s law of diffusion.13 Rentsch, R. Preu, and S. W. Glunz, Sol. Energy Mater. Sol. Cells 93, 1074
Because the diffusion of silicon in the liquid aluminum 共2009兲.
4
S. M. Yang and J. Pl, Solid-State Electron. 53, 925 共2009兲.
proceeds laterally within the aluminum layer, a large amount 5
H. Plagwitz and R. Brendel, Prog. Photovoltaics 14, 1 共2006兲.
of aluminum should overlap each side of the dielectric open- 6
J. Müller, K. Bothe, S. Gatz, F. Haase, C. Mader, and R. Brendel, J. Appl.
ing to achieve an optimal metal–semiconductor interaction. Phys. 108, 124513 共2010兲.
7
This overlapping of aluminum on narrow dielectric openings A. Urueña, J. L. Hernández, J. John, J. Poortmans, and R. Mertens, Pro-
is evident due to the reduction in the contact resistivity and ceedings of 25th EUPVSEC, Hamburg, Germany, 2010, pp. 2562–2564.
8
F. S. Grasso, L. Gautero, J. Rentsch, R. Preu, and R. Lanzafame, Proceed-
the homogeneous formation of the local BSF.10 We suggest ings of 25th EUPVSEC, Hamburg, Germany, 2010, pp. 371–374.
that the maximum spread limit of diffused silicon, d2, may 9
J. Krause, R. Woehl, and D. Biro, Proceedings of 25th EUPVSEC, Ham-
determine the minimum width of the aluminum metallization 10
burg, Germany, 2010, pp. 1899–1904.
needed for an optimal contact and full local BSF formation. E. Urrejola, K. Peter, H. Plagwitz, and G. Schubert, J. Appl. Phys. 107,
124516 共2010兲.
Thus, the aluminum overlapping is determined by d2. In this 11
W. van Gelder and V. E. Hauser, J. Electrochem. Soc. 114, 869 共1967兲.
way, the finger spacing may also be determined by the spread 12
V. A. Popovich, M. Janssen, I. M. Richardson, T. van Amstel, and I. J.
limit of silicon in the screen-printed aluminum layer 共L p Bennett, Sol. Energy Mater. Sol. Cells 95, 93 共2011兲.
13
ⱖ d2兲. Another application of the aluminum overlapping may P. G. Shewmon, Diffusion in Solids 共McGraw-Hill, New York, 1963兲, pp.
9–14.
be found on interdigitated back-contact n-type silicon solar 14
V. D. Kurochkin, L. P. Kravchenko, L. N. Kuz’menko, and L. A. Tsurpal,
cells to obtain high-quality screen-printed aluminum-alloyed Powder Metall. Met. Ceram. 44, 191 共2005兲.
15
emitters. A. Paccagnella, G. Ottaviani, P. Fabri, G. Ferla, and G. Queirolo, Thin
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16
J. O. McCaldin, Appl. Phys. Lett. 19, 524 共1971兲.
contact formation between an screen-printed aluminum 17
T. Lauermann, T. Lüder, S. Scholz, B. Raabe, G. Hahn, and B. Terheiden,
paste and narrow silicon contact areas. The spread of Proceedings of 35th IEEE PVSC, Hawaii, USA, 2010, p. 000028.
18
silicon in a screen printed aluminum layer increases by A. Paul, Ph.D. thesis, Technische Universiteit Eindhoven, 2004.
19
共1.5⫾ 0.06兲 m / ° C when increasing the peak firing tem- E. O. Kirkendall, Trans. AIME 147, 104 共1942兲.
20
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22
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