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Solar Energy Materials 2 (1979/1980) 265-275

North-Holland Publishing Company

LARGE G R M N SILICON FILMS ON METALLURGICAL


SILICON SUBSTRATES
FOR PHOTOVOLTAIC APPLICATIONS*

T. L. CHU, Shirley S. CHU, and E. D. STOKES


Southern Methodist University, Dallas, TX 75275, USA

Received 14 November 1979

Metallurgical silicon at a cost of about $1/kg is an economical substrate for the deposition of
silicon films for photovoltaic applications. To prepare the substrate, pulverized metallurgical silicon,
purified by acid-extraction and phosphorus pentoxide treatment, was recrystallized on graphite by
unidirectional solidification and zone-melting. The structural and crystallographic properties of
metallurgical silicon substrates prepared at different rates of solidification were investigated. Silicon
films of controlled electrical resistivity were deposited on metallurgical silicon substrates by the
thermal reduction of trichlorosilane containing appropriate dopants. The concentration and distribu-
tion of metallic impurities, Hall mobilities, potential barriers and minority carrier diffusion length
profile in these films were investigated. Solar cells of 9 cm 2 area were prepared from silicon films of
25-30/~m thickness containing a p-n junction. By using a drift field in the surface region and a back
surface field at the silicon film/substrate interface, AM1 efficiencies of up to 9.75~ have been obtained.

1. Introduction

The current interest in the terrestrial utilization of solar energy by photovoltaic


converters has stimulated considerable research and development efforts, on low
cost solar ceils. The use of thin semiconductor films on a low cost substrate has been
considered as a promising approach to reduce the material and processing costs of
solar cells. In the thin film approach, the selection of substrates is an important
consideration. An ideal substrate must be compatible with the semiconductor in
chemical and mechanical properties, must provide a low resistance electrical contact
to the active region, and must not introduce impurities into the active region. In the
case of indirect-gap materials with a gradual optical absorption edge, such as silicon,
the structural properties of the substrate is also important in that the deposited films
should have relative large grains, 100 #m or larger, in order to achieve reasonable
conversion efficiencies.
A number of polycrystalline and amorphous foreign substrates have been used for
the deposition of silicon films by chemical and physical vapor deposition techniques.
The microstructure of the deposit has been found to depend, in essentially all cases,

*Prepared for the Division of Solar Technology, Department of Energy under contract No. EY-76-
C-03-1285.

265
266 T. L. Chu et al, / Lar#e #rain silicon films on metalluryical silicon substrates

on the structural properties of the substrate; however, the grain size in films of
limited thickness is usually small, less than 25 #m [1]. Silicon films have beeffdeposited
on several foreign substrates, such as aluminum [2], borosilicate-coated steel [3],
graphite [4] and titanium boride-coated alumina [5], for solar cell purposes by
chemical vapor deposition and vacuum evaporation techniques. All films have been
found to consist of small grains, and solar cells prepared from these films have low
conversion efficiencies due to the recombination of light-generated carriers at grain
boundaries. To improve the conversion efficiency of polycrystalline thin film silicon
solar cells, the grain size in the silicon films must be substantially increased or the
effects of grain boundaries minimized. Since the solidification of a silicon melt often
yields large crystallites, metallurgical grade silicon with a cost of $1/kg is an attractive
substrate for the deposition of silicon films. Partially purified and unidirectionally
solidified metallurgical silicon has been used in our laboratory as a substrate for the
deposition of silicon films and the fabrication of solar cells.
In this work, the chemical, structural, electrical and photovoltaic properties of
silicon films deposited on unidirectionally solidified metallurgical silicon substrates
have been studied. The experimental procedures and results are discussed in this
paper.

2. Preparation and properties of metallmgical silicon substrates

Pulverized metallurgical grade silicon with an iron content of about 0.35~o was
purified by a two-step process: (1) extraction with aqua regia, and (2) treatment with
phosphorus pentoxide. The acid-extraction technique is based on the facts that the
major portion of metallic impurities precipitates at grain boundaries during the
solidification of molten metallurgical silicon in the manufacturing process and that
the pulverization of metallurgical silicon takes place at grain boundaries. By reflexing
pulverized metallurgical silicon with aqua regia until the supernatant becomes
colorless, the concentration of iron in metallurgical silicon has been found to be
reduced to 600-800 ppma. The acid-extracted material was further purified by heat
treatment with phosphorus pentoxide. The gettering of low concentration of metallic
impurities from silicon devices by phosphorus pentoxide has been shown to con-
centrate the impurities in the n + surface region and the oxide glass [6]. Because of
the high concentration of metallic impurities, metallurgical silicon was mixed with
about 3-5~o of phosphorus pentoxide and heated at 1050C for 4-5 days. This
treatment has been found to further reduce the iron concentration in metallurgical
silicon to 200-250 ppma.
Metallurgical silicon substrates were prepared by the unidirectional solidification
[7] or zone-melting [8] of the partially purified material on a graphite plate in a
hydrogen atmosphere. The rate of solidification has been found to be the most
important parameter affecting the structural properties of the substrate. At high
rates of solidification, 2-5 cm/min, the surface of solidified material is non-planar
with many ridges, faces and valleys. The surface of the substrate becomes planar by
reducing the rate of solidification to 1 cm/min or less.
T. L. Chu et al. / Large #rain silicon films on metallurgical silicon substrates 267

Figs. 1 and 2 show, respectively, the optical and scanning electron micrographs
of the surface of a substrate with a non-planar surface, illustrating its unique appear-
ance with ridges, faces and valleys. The crystallites are elongated, up to 10 cm in
length and several millimeters in width. All ridges are extremely straight, suggesting
that they are the intersections of twin planes with the grown surface. When a specimen
is cross-sectioned vertically perpendicular to a ridge and the cross sectioned surfaces

A'~Y

Fig. 1. Optical photograph of the non-planar surface of a metallurgical silicon substrate showing ridges,
faces and valleys.

VAL!.EY FACE R[D(;E

Fig. 2. Scanning electron micrograph of the non-planar surface of a metallurgical silicon substrate showing
ridges, faces and valleys.
268 T. L. Chu et al. / Large grain silicon films on metallurgical silicon substrates

mechanically polished and chemically etched, etch traces of twin planes are revealed,
as shown in fig. 3. Most valleys are curved and are high angle grain boundaries. The
X-ray diffraction technique was used to determine the crystallographic orientations
of the faces of crystallites. The commonly observed orientations are {331}, {531 },
and high index planes from the twinning of {331} and {531} planes about a {ill}
plane. The twinning of the (331) and (531) planes about the (1-11) plane yields (11 7 1)
and (13, 11, 5) planes, respectively. The angle between (331) and (11 7 1) is 164.8',
and that between (531) and (13 11 5) is 172.4. In many cases, the measured angle
between the two faces adjacent to a ridge is about 165. Chemical etching has also
revealed that the crystallites are usually multiple-twinned and the dislocation density
varies widely from face to face.
The metallurgical silicon substrates with planar surfaces also consist of elongated
crystallites up to several centimeters in length. Chemical etching has revealed twin
planes, grain boundaries and dislocation clusters as the most common defects.
Fig. 4 shows the etched surface of an area with relatively high defect density, where
the etch traces of twins and grain boundaries are apparent. X-ray diffraction examina-
tions indicate that some areas show a very strong {110} preferred orientation while
others a very strong {331} preferred orientation.
Metallurgical silicon substrates are n-type with an electrical resistivity of 0.02-
0.03 ~ cm. Spreading resistance measurements indicate that the resistivity is relatively
uniform along the length of the specimen, 15 cm. To determine the iron distribution
in the substrate along the direction of solidification, the substrate was cut into twelve
pieces of about equal length, and the concentration of iron in silicon on each piece
was determined. Both slowly and rapidly solidified specimens were analyzed.
Although considerable segregation of iron is expected in slowly solidified material,
the segregation was found to be negligible in both cases. The concentration of iron

Fig. 3. Polished and etched surface of the vertical cross section of a metallurgical silicon substrate with a
non-planar surface cut perpendicular to a ridge.
T. L. Chu et al. / Large grain silicon films on metallurgical silicon substrates 269

Fig. 4. Etched surface of a planar metallurgical silicon substrate showing grain and twin boundaries.

varied less than a factor of three along the length of the specimen. This is due probably
to the high diffusion coefficient of iron in silicon at high temperatures, and the
segregated impurities diffuse back into the solidified material.

3. Impurities in silicon films

Silicon films of controlled thickness and resistivity have been deposited on metal-
lurgical silicon substrates at 1100-1150 C by the thermal reduction of trichlorosilane
containing appropriate dopants, phosphine or diborane, in the usual manner [4].
The deposition rate was 0.2-2/zm/min, depending on the thickness required, and
was controlled by the concentration of trichlorosilane in the reactant mixture. In all
cases, the deposited silicon was found to be epitaxial with respect to the substrate
by. metallographic examinations.
Since metallurgical silicon substrates contain a high concentration of iron and iron
diffuses rapidly at temperatures used for the deposition of silicon films, the con-
centration profile of iron in the thickness direction of the film was determined. A
specimen with a silicon film of about 25 #m thickness on metallurgical silicon sub-
strates was used. The silicon film was dissolved at about 2/~m intervals, and the iron
concentration in each solution was found to be essentially the same, similar to the
iron concentration in the substrate, about 200 ppma. Thus, iron has diffused from
the substrate through the silicon film during the deposition process.
The results of chemical analysis indicate that the concentration of iron in silicon
films far exceeds the solubility of iron in silicon at room temperature. Thus, the
silicon films become supersaturated with iron, and the excess iron should precipitate.
By forming a shallow p-n junction in the silicon film during the deposition process
and examining the resulting film with a scanning electron microscope in the electron
beam induced current (EBIC) mode, the presence of impurity precipitates has been
270 T. L. Chu et al. / Large grain silicon.[i/ms on metallurgical silicon substrates

observed. Fig. 5 shows the EBIC micrograph of one region of a shallow p - n junction
structure on a metallurgical silicon substrate. All grain boundaries are clearly
delineated because of the reduced collection of beam-induced current. In addition,
there are numerous small dots in the grains showing varying degrees of low collection
efficiency. These dots are most likely impurity precipitates since they redistribute
after heat treatment. Fig. 6 shows the EBIC micrograph of the same region as shown
in fig. 5 after heat treatment at 950C for 0.5 h, where a noticeable fraction of the
impurity precipitates has diffused to structural defects such as grain boundaries.

4. Hall mobility and potential barriers in silicon films

Since metallurgical silicon substrates are of n-type conductivity, p-type silicon


films were deposited for ease of characterization. The Hall mobilities in several

Fig. 5. EBIC micrograph of one region of a shallow p n junction structure on a metallurgical silicon
substrate showing impurity precipitates.

Fig. 6. EBIC micrograph of the same region in fig. 5 after heat treatment at 950"C for 0.5 h.
T. L. Chu et al. / Large grain silicon films on metallurgical silicon substrates 271

silicon films were measured at room temperature by the van der Pauw technique.
The specimens were about 1 x 1 cm 2 in area and contained one or more grain bound-
aries. Four contacts were made to the silicon layer along the circumference of the
specimen by evaporating titanium and silver through a metal mask followed by
annealing in hydrogen at 525C. Current was passed between two alternating con-
tacts, and the change in potential between the other two contacts due to the magnetic
field was measured. The resistivity, Hall mobility, and carrier concentrations were
then calculated from the Hall voltage. Reproducible results were obtained only in
specimens with carrier concentrations higher than about 1017 cm - 3, and the measured
mobilities were slightly lower than those in single crystalline silicon of similar carrier
concentrations. At lower carrier concentrations, however, the results were erratic
and irreproducible due to the potential barriers at grain boundaries.
The potential barriers at grain boundaries in silicon films were investigated by
using a high resolution potential probe apparatus. The p/n specimens were cut
into strips of about 0.3 cm width and 1.5 cm length, and the cutting was carried out
in such a manner that twin and grain boundaries were approximately parallel to the
width of the specimen. Current contacts were then applied to both ends of the long
dimension by evaporating titanium and silver through a metal mask followed by
annealing, and lead wires were attached to the contacts by using conducting epoxy.
The specimen was mounted on the mechanical stage of a toolmaker's microscope,
where its position can be controlled with an accuracy of 0.01 mm by two micro-
meters. Since the direction of the current flow was approximately perpendicular to
twin and grain boundaries, the potential variation along the current path was
measured by using a fixed contact (one current contact) and a moving probe. The
moving probe had a radius of curvature of 2.5 10-3 cm at its tip and was supported
in such a manner that it could be readily placed on the surface of the specimen with a
known fixed force without dragging. A measurable voltage drop was observed at all
grain boundaries; the magnitude of the voltage drop increases rapidly with the
resistivity of the silicon film and becomes appreciable in materials of 0.2 f2 cm resisti-
vity or higher. Fig. 7 shows the potential gradient in a p-type film of 1 f2 cm resistivity,
where the measurements were carried out at 25 #m intervals and at two current levels,
100/~A and 50/~A. The change in potential gradient at grain boundaries are very
pronounced ; however, the potential drop is not directly proportional to current and
also depends on the direction of current flow.

5. Minority carrier diffusion length in silicon films

Minority carrier diffusion length is an important parameter affecting the operation


of most silicon devices. Since silicon is an indirect-gap material, the recombination
of hole--electron pairs takes place mainly via defect centers. In view of the high
concentrations of chemical and structural defects in silicon films deposited on
metallurgical silicon substrates, the minority carrier diffusion length is expected to
be short, particularly at and near grain boundaries.
The minority carrier diffusion length in a number of silicon films of 0.2-0.5 f~ cm
272 T. L. Chu et al. / Large grain silicon,films on metallurgical silicon substrates

I00 pAI

I I I I I I I I I I I
1 2 3 4 5 6 7 8 9 10 11
DISTANCE, MILLIMETER
Fig. 7. Potential gradient as a function of probe position in a p-type silicon film of 1 f~ cm resistivity on
a metallurgical silicon substrate.

resistivity and 25-30 pm thickness was measured by the steady state surface photo-
voltage method [9] using the apparatus described previously [10]. In this method,
the surface of the specimen is illuminated with chopped monochromatic radiation
with energy slightly higher than the energy gap of silicon. The photo-generated
electron-hole pairs diffuse to the surface and are separated by the electric field of the
depletion region to produce a surface photovoltage. The surface photovoltage is
measured as a function of the wavelength, and the incident light intensity is adjusted
to produce the same value of surface photovoltage. It has been shown that the light

.-o
12
o

F~ 8

4
I I I I I I I I I I
2 4 6 8 I0 12 14 16 18 20
DISTANCE,MILLIMETER
Fig. g. Diffusion length profile across the width of a silicon film deposited on a metallurgical silicon sub-
strate.
T. L. Chu et al. / Large grain silicon films on metallurgical silicon substrates 273

{d

oo

~=~

O'~

o.=

~:~ o

d~

intensity is a linear function of the reciprocal absorption coefficient for each wave-
length and that the extrapolation of this linear plot to zero intensity yields diffusion
length as the negative intercept. However, the thickness of the film must be greater
than four times the diffusion length; otherwise, the measured diffusion length is the
"effective diffusion length".
The diffusion length profile across the width of a number of silicon films has been
measured. The diameter of the light beam is about 0.5 mm by using a mask, and the
measurements were carried out at 2 mm intervals. All specimens have been found to
274 T. L. Chu et al. / Large yra& silicon,films on metalluryical silicon substrates

show diffusion length inhomogenieties, and the decrease in diffusion length is most
pronounced at grain boundaries. Fig. 8 shows an example of a diffusion length profile,
where the range of effective diffusion length is 7-13/~m, and the low diffusion length
regions are often associated with structural defects.

6. Photovoltaic applications of silicon films

Silicon films containing a p-n junction deposited on metallurgical silicon sub-


strates have been used for the preparation of solar cells. Since the substrate is 0.02-
0.03 f~ cm n-type, the deposited film is of the p/n configuration, and the substrate
also provides a back-surface field. The n-region is usually of 0.2-0.5 fl cm resistivity
and 25-30 #m thickness, and the p region is 1.5-2 #m thickness and has a graded
dopant profile to provide a drift field. The sheet resistance of the p + region is 40-60
f~/~, and the spreading resistance profile appears to be linear with a surface resistivity
of 0.003-0.005 ~ cm.
In many cases, the solar cell structures were heated at 850-950~C in a hydrogen
atmosphere before the contacting process ; hydrogen was used because its purification
by diffusion through a palladium-silver alloy provides the puriest inert gas available
in the laboratory. The graphite plate serves as the ohmic contact to the n-region,

30 I CELLAREA: 9 CM2
AR COATING: Sn02
FILL FACTOR: 74.(g~
AMI EFF: q. 75%
25

20

I I I I I I
0.1 0.2 0.3 0.4 0.5 0.6
VOLTAGE,V
Fig. 10. Current-voltage characteristics of a thin film silicon solar cell under illumination at AM1 con-
ditions.
T. L. Chu et al. / Large grain silicon films on metallurgical silicon substrates 275

and the grid contact of titanium and silver was made in the usual manner. The deposi-
tion of approximately 700 ,~ of tin oxide at 400C serves as the antireflection coating.
Invariably, solar cell structures subjected to heat treatment after the deposition
process showed higher conversion efficiencies than those without heat treatment.
It is possible that the dopant in the p +-region has diffused along grain boundaries
and into the surface of grains to form vertical p-n junctions, thus converting the
recombination boundaries into charge collection boundaries. The EBIC technique
was used for the evaluation of the effects of heat treatment. Improvements in the
collection of beam-induced currents at grain boundaries were observed in some cases.
An example is shown in fig. 9 where the EBIC photograph (10 keV electron energy)
of one region of a solar cell after heat treatment at 850C and the associated line
scan are reproduced to show the enhanced current collection at grain boundaries.
However, such enhancements are not always observed. This may be due to the
precipitation of metallic impurities at structural defects masking the charge collection
effects of vertical p-n junctions.
The best solar cells (9 cm 2 area) have an AM1 efficiency of 9.75~. An example is
shown in fig. 10, reproducing the current-voltage characteristics of a solar cell under
illumination with GE ELH quartz-halogen lamps at AM1 conditions.

References

[1] See, for example, E. G. Bylander and M. M. Mitchell, Metallurgy of Advanced Electronic Materials,
vol. 19, ed. G. E. Brock (Interscience, New York, 1962) p. 293 ; T. I. Kamins and T. R. Cass, Thin
Solid Films 16 (1973) 147.
[2] P. H. Fang, L. Ephrath and W. B. Novak, Appl. Phys. Lett. 25 (1974) 583.
[3] T. L. Chu, H. C. Mollenkopf and S. S. Chu, J. Electrochem. Soc. 122 (1975) 1681.
[4] T. L. Chu, H. C. Mollenkopf and S. S. Chu, J. Electrochem. Soc. 123 (1976) 106.
[5] C. Feldman, H. K. Charles, F. G. Satkiewicz and N. A. Blum, in: Conf. Record 12th IEEE Photo-
voltaic Specialists Conf., Baton Rouge, LA (November 1976) p. 100.
[6] S. P. Murarka, J. Electrochem. Soc. 123 (1976) 765.
[7] T. L. Chu, S. S. Chu, K. Y. Duh and H. I. Yoo, IEEE Trans. Electron Devices ED-24 (1977) 442.
[8] T. L. Chu, S. S. Chu, K. Y. Duh and H. C. Mollenkopf, J. Appl. Phys. 48 (1977) 3576.
[9] A. M. Goodman, J. Appl. Phys. 32 (1961)2550.
[10] T. L. Chu and E. D. Stokes, in : Conf. Record 13th IEEE Photovoltaic Specialists Conf., Washington,
DC (June 1978) p. 95.