ELECTRON MICROSCOPY ANALYSIS OF SILICON ISLANDS AND LINE STRUCTURES FORMED ON SCREEN-PRINTED AL-DOPED P+-SURFACES

Robert Bock , Jan Schmidt , Rolf Brendel , Henning Schuhmann , and Michael Seibt
Institut fr Solarenergieforschung Hameln (ISFH), Am Ohrberg 1, 31860 Emmerthal, Germany
2
IV.Physikalisches Institut, Georg-August-Universitt Gttingen, Friedrich-Hund-Platz 1, D-37077 Gttingen,Germany
1

ABSTRACT

EXPERIMENTAL
+

Islands and line networks of aluminum-doped p regions formed in a conventional screen-printing process
are investigated by a combination of different techniques.
To characterize the microscopic nature of the islands (lateral dimensions 1-3 m) and line networks of selfassembled nanostructures (lateral dimension 50 nm)
advanced transmission electron microscopy (TEM), scanning electron microscopy (SEM), scanning transmission
electron microscopy (STEM) and energy dispersive X-ray
analysis (EDX) are combined. Aluminum inclusions are
detected 50 nm below the surface of the islands and crystallographic aluminum precipitates of < 7 nm in diameter
are found within the bulk of the islands. In addition, aluminum inclusions (lateral dimension ~30 nm) are found
within the bulk of the self-assembled line networks. Our
findings provide clear experimental evidence that the concentration peak generally measured at the surface of
+
screen-printed Al-p regions is due to the microscopic
structures formed on the silicon surface during the firing
process.

We use single-crystalline shiny-etched (100)-oriented

300 m thick p-type float zone (FZ) silicon wafers of 200
cm resistivity. The samples are prepared by screenprinting the Al-paste on one side of the Si wafer with an
2
amount of 8 mg/cm . After drying the screen-printed samples at 150 C for 5 min to vaporize the organic solvents
+
in the Al-paste, the Al-p region is formed in an infrared
conveyor belt furnace at 900C for 13 seconds. In order to
+
investigate the p surface, the residual aluminum paste
and the aluminum-silicon eutectic are removed from the
+
Al-p region in a boiling 37% solution of hydrochloric acid.
For an advanced analysis of the structures which remained on the aluminum-doped surface after solidification
of the aluminum-silicon eutectic liquid, we use electron
microscopy techniques including scanning transmission
electron microscopy (STEM) in combination with energy
dispersive X-ray analysis (EDX), transmission electron
microscopy (TEM) and high resolution transmission electron microscopy (HRTEM). Sample cross sectioning is
performed by focused ion beam (FIB) thinning.
RESULTS AND DISCUSSION

INTRODUCTION
+

Screen-printed aluminum-doped p (Al-p ) regions

formed on crystalline silicon wafers are mainly used as
back surface field (BSF) in p-type crystalline silicon solar
cells [1,2] and as rear side emitter in screen-printed back
junction n-type crystalline silicon solar cells [3]. From doping profiles measured by the electro-chemical capacitance
voltage (ECV) or the secondary ion mass spectroscopy
+
(SIMS) method it is known that such screen-printed Al-p
regions typically show a doping concentration peak close
to the surface, which is not consistent with the solid solu+
bility data of Al in Si [4,5]. During processing of Al-p regions from screen-printed Al thick-films, the abrupt solidification of the liquid Al-Si eutectic composition forms islands and line networks. In previous publications it was
conjectured that the observed concentration peak at the
surface probably originates from these residual aluminum+
rich silicon structures on the Al-p surface [6,7,8], however, the reason for the observed peak was never investigated in detail. In this contribution, we combine state-ofthe-art electron microscopy techniques to reveal the nature of the islands and line networks observed on screen+
printed Al-p regions.

Figures 1 (a-b) show EDX elemental mappings of Si,

Al, and Pt measured on the surface island depicted in Fig.
2 (b). An increased aluminum signal at three positions labeled 1, 2, and 3 in Fig 1 (b) can be observed. A closer
look at position 2 shows a clear aluminum signal (see Fig.
1 (g)) underneath the silicon signal (see Fig. 1 (f)) indicating a thin silicon capping layer on top of residual Al-rich
material. The observed platinum signal surrounding the
silicon island shown in Figs. 1 (c) and (e) stems from the
FIB preparation method.
Figure 2 (a) shows a tilted plan view SEM secondary
+
electron image of the Al-p surface after the residual Al
paste and the Al-Si eutectic have been removed in boiling
37% HCl solution. The investigated islands and line net+
works appear as bright contrast on top of the dark Al-p
surface. The typical lateral dimension of the islands
ranges from 1-3 m. The islands are arranged along a
line network of nanostructures (lateral dimension ~50 nm).

Fig. 1 (a-c) EDX Elemental mappings of the Si, Al and the Pt intensity measured on the surface island shown in Fig. 2
(b). (d) Cross-sectional dark-field STEM image of position 2. (e - g) Elemental mappings of the Pt, Si and the Al intensity
at position 2.
80

(a)

Scan 1

Al

60

Counts

Almost all surface structures show crystallographic

facets with a pyramid-like geometry. Figure 2 (b) shows a
cross-sectional TEM bright field image of a typical surface
structure prepared by the FIB method. From this image no
defects such as dislocations or grain boundaries can be
found within the bulk of the island. The island is completely defect-free and of the same crystallographic orien+
tation as the Al-p bulk and thus epitactic.

Si

40

scan
direction

20

0
0

50

100 150 200 250 300

Position [nm]
60

Si

Scan 2

(b)

Fig. 2 (a) SEM tilted plan-view image of an Al-p surface

after the residual Al-paste and the Al-Si eutectic have
been removed. Islands and line networks appear as bright
contrast. b) Cross-sectional TEM bright-field image of one
individual island. The sample is prepared using the focused ion beam method. Lines labeled 1 and 2 indicate
positions of EDX line scans shown in Fig. 3 (a) and (b).
For a detailed investigation of the Al-rich regions, an
EDX line scan analysis is performed along the lines at position 1 and 2 from Fig. 2 (b).
Figure 3 (a) shows the EDX line scan 1 from Fig. 2 (b).
An aluminum signal 50 nm below the silicon signal is
clearly visible. From this we conclude that Al-rich material
is covered by a thin layer of Si-rich material. Figure 3 (b)
shows the EDX line scan 2, where 4 Al peaks on both
sides of the Si peak can be observed.

Counts

50

scan
direction

Al

40

Al

Al

Al

30
20
10
0
0.0

0.2

0.4

0.6

0.8

1.0

Position [m]
Fig. 3 (a) EDX line scan along line 1 of Fig. 2 (b). A clear
aluminum signal can be identified on the left hand side of
the silicon island; the Al layer is covered by a further silicon layer indicated be the left-most silicon peak. (b) EDX
line scan along line 2 of Fig. 2 (b). Four Al peaks are visible revealing the lamellar microstructure reminiscent of
the Al:Si eutectic.

residual Al-Si eutectic, which was not etched off in boiling

HCl due to its protected location.

Fig. 4 Cross-sectional STEM bright-field image of a nano+

line structure on top of the Al-p surface. The line labeled
3 indicates the position of the EDX line scan.
The TEM bright field image shows a lamellar geometry
at the Al-rich positions. This leads to the conclusion that
these small lamellar Al-rich inclusions at both positions
can be attributed to residual Al-Si eutectic, which could
not be removed in boiling HCl, because they are covered
by a thin layer of crystalline Si (see line scan 1) or by the
island itself (see line scan 2).

100

Figure 6 shows a more detailed bright field TEM image

taken near the surface of the island shown in
Fig. 2 (b). Numerous dark spots (highlighted by arrows)
can be observed within the silicon matrix. From the high
resolution TEM image of one selected dark spot shown in
Fig. 7 a clear Moir pattern can be identified, which is attributed to the lattice mismatch between the Al-precipitate
and the Si-matrix. Thus, we conclude the precipitates to
be crystalline and fully incorporated into the silicon matrix.

Scan 3

Counts

80
60

Al Si

40
+

Al-p
bulk

20

Fig. 6 Cross-sectional TEM bright field image showing

precipitates as dark dots within the crystalline silicon bulk
of the surface structures.

scan
direction

0
0

20 40 60 80 100 120 140 160

Position [nm]
Fig. 5 EDX line scan along line 3 of Fig. 4, indicating that
Al-rich material is covered by a thin layer of Si.
Figure 4 shows a cross-sectional STEM image of one
+
line of the self-assembled line network on the Al-p surface. From this image we determine the structure width to
be ~50 nm and the height to be ~26 nm. The EDX line
scan along line 3 of Fig. 4, which is depicted in Fig. 5
shows an Al signal underneath the Si signal. Again, we
observe that there is Al-rich material covered by a thin Si
layer, which prevents the Al-rich material to be etched in
boiling HCl.
In summary, we found aluminum-rich inclusions of
about 30 nm in diameter roughly 10-20 nm below the Si
surface of the observed islands. Aluminum-rich inclusions
of lamellar geometry were identified in cavities below the
entire island. The self-assembled network of nanostructures also shows aluminum-rich inclusions covered by a
silicon layer. We attribute all found Al-rich inclusions to

Fig. 7 Cross-sectional HRTEM image of a crystalline precipitate within the crystalline Si matrix of an island on the
+
Al-p surface. The precipitate is fully embedded into the
silicon matrix (Moir-contrast due to different lattice constants).
From the HRTEM micrograph the diameter of the precipitates was determined to be 7 nm. The precipitates
are also analyzed by the EDX method, showing that they
consist of crystalline aluminum.

-3

Aluminum dopant density [cm ]

aluminum doping profile after a 15 s etching step in an

HNO3/CH3COOH/HF (6:1:1 composition) solution is
shown. The surface concentration peak is completely removed by the short etching step, whereas the total profile
depth and concentration characteristics are the same as
before the etching.

Fig. 8 Cross-sectional dark-field STEM image of two crystalline precipitates appearing as bright spots. The line labeled 4 indicates the position of the EDX line scan
shown in Fig. 9.
Figure 8 shows a cross-sectional STEM dark-field image of two precipitates appearing as bright spots which
were analyzed with the EDX method. The corresponding
EDX line scan along line 4 of Fig. 8 is shown in Fig. 9 indicating an enhanced Al-signal at positions of the bright
spots from the STEM signal. From this correlation it can
be concluded that the precipitates are highly Al-rich.
However, this analysis does not show chemical compositions, particularly the precipitates are fully embedded into
the silicon matrix making a quantitative EDX analysis
more difficult, and hence it is not clear if this is metallic
aluminum, a silicate or any other crystalline Al-rich composition.

Normalized Counts

1.2

Scan 4

1.0

non etched Al-p emitter

10

19

10

18

10

17

Al-p emitter

Etched Al-p emitter

(15 sec. dip)

Printed amount
2
of Al paste: 8 mg/cm

10

16

6
8
Depth [m]

10

12

Fig. 10 Doping profiles of the same screen-printed Al-p

sample. Comparison of the doping profile before and after
a 15 s etching step, measured by the ECV method. During the etching, the Al-rich islands and line-networks on
the surface are removed. The profile after etching shows
no concentration peak at the surface.
Based on the experimental results in this work it can
be concluded that the aluminum inclusions beneath the
silicon surface and the aluminum precipitates within the
islands and line-networks on the surface are the cause for
the observed aluminum doping concentration peak at the
+
surface of screen-printed Al-p regions.

0.8

scan
direction

Si

0.6

CONCLUSIONS

Al-precipitate

0.4
0.2
0.0
0

10

20

30

40

50

60

Position [nm]
Fig. 9 EDX line scan along line 4 of Fig. 8 showing an
enhanced Al-signal at positions of the Al-precipitates depicted in Fig. 8.
The nano-precipitates are only present within the bulk
of the islands but can not be observed in the bulk of the
+
Al-p region, which indicates a completely defect-free Al+
p region.
Figure 10 shows a typical aluminum doping profile
measured by ECV after the residual Al paste and the Al-Si
eutectic have been removed in boiling HCl. In addition, an

In conclusion, we have clarified the origin of the surface concentration peak present in doping profiles of
+
screen-printed Al-p regions measured by the ECV and
the SIMS technique. Aluminum inclusions were found 50
nm beneath the silicon surface of islands and linenetworks which remain after removal of the residual Al
paste and the Al-Si eutectic in boiling HCl. Using HRTEM,
STEM and EDX analysis, aluminum precipitates of 7 nm
diameter were localized within the bulk of the islands on
+
the Al-p surface. Additionally, aluminum inclusions of
about 30 nm in diameter covered by a thin silicon layer
were found within the self-assembled network of line-like
+
nanostructures on the Al-p surface. After removal of the
residual aluminum-rich silicon surface structures, the Al
concentration peak at the surface measured by ECV and
SIMS completely disappeared.
Acknowledgments
Funding was provided by the State of Lower Saxony and
the German Ministry for the Environment, Nature Conser-

vation and Nuclear Safety (BMU) under Contract No.

0327666.

REFERENCES
[1]
[2]
[3]

[4]
[5]
[6]
[7]

[8]

G. C. Cheek, R, P. Mertens, R. Van Overstraeten,

and L. Frisson, IEEE Trans. Electron Devices, ED31, 602 (1964).
C.F. Gay, in Proceedings of the 13th IEEE Photovoltaic Specialists Conference, p. 444, IEEE
(1978).
Cuevas A, Samundsett C, Kerr MJ, Macdonald DH,
Mckel H, Altermatt PP. Proceedings of the 3rd
World Conference on Photovoltaic Solar Energy
Conversion, Osaka, Japan, 2003, p. 963.
J.L. Murray, A.J. McAlister, Bull. Alloy Phase Diagrams, 5 (1), 74 (1984).
F.A. Trumbore, Bell Syst. Tech. J. 39 205 (1960).
P. Llgen and C. Leguijt, Proceedings of the 23th
IEEE Photovoltaic Specialists Conference, Louisville, USA, (IEEE, New York, 1993), p. 236.
P. Llgen, W. C. Sinke, C. Leguijt, A.W. Weeber,
P. F. A. Alkemade, and L. A. Verhoef, Appl. Phys.
Lett. 65, 2792 (1994).
th
F. Huster, and G. Schubert, Proceedings of the 20
European Photovoltaic Solar Energy Conference,
Barcelona, Spain (WIP, Munich, 2005), p. 1462.