Materials Technology

Advanced Performance Materials

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Influence of doping and microstructure on

electrical properties of doped silicon thin films

Y. Lu, H. Li, G. Yang & B. Jiang

To cite this article: Y. Lu, H. Li, G. Yang & B. Jiang (2015) Influence of doping and microstructure
on electrical properties of doped silicon thin films, Materials Technology, 30:1, 28-32, DOI:
10.1179/1753555714Y.0000000195

To link to this article: http://dx.doi.org/10.1179/1753555714Y.0000000195

Published online: 25 Sep 2014.

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 Influence of doping and microstructure on
electrical properties of doped silicon thin films
Y. Lu1, H. Li*1, G. Yang1 and B. Jiang2
In this work, phosphorus and boron doped silicon films were deposited on monocrystalline silicon
substrates by plasma enhanced chemical vapour deposition. Microstructure and net doping
concentration were investigated using Raman spectroscopy and secondary ion mass spectro-
meter, and the dark conductivity, carrier concentration and mobility of the films were measured
using semiconductor characterisation system. The results indicated that the structure of the films
were all amorphous despite of the different doping gas flow ratios, and the dark conductivity and
carrier density changed by only one order of magnitude with the increase in [PH3]/[SiH4] and
[B2H6]/[SiH4] gas flow ratios. The best flow ratios of [PH3]/[SiH4] and [B2H6]/[SiH4] were obtained
to be 1?5 and 1% respectively, and then the optimised samples were annealed. After annealing,
the film expressed a tendency of transition to crystalline from amorphous according to the Raman
results, and the dark conductivity and carrier concentration increased by two to three orders of
magnitude for both doped film series. The structure has more significant influence on the
electrical properties of doped silicon thin film than the doping concentration.
Keywords: Silicon thin film, Doping, Annealing, Microstructure, Electrical properties

Introduction However, it has been recognised that a-Si:H thin films

Amorphous silicon (a-Si) thin film solar cells have
dominated the development of thin film photovoltaic
(PV) modules and demonstrated the potential for lower
cost production than crystalline silicon (c-Si).1–4 The
advantage of a-Si over c-Si is in the much higher
absorption coefficient enabling high absorption of solar
radiation for a film thickness of the order of 1 mm
compared with 200 mm for c-Si.
The amorphous structure of non-hydrogenated amor-
phous silicon (a-Si) leaves dangling bonds from fourfold
coordinated silicon atoms, and these are passivated with
hydrogen, often referred to as hydrogenated amorphous
silicon (a-Si:H). Comparing with a-Si, a-Si:H has lower
density of band gap. It is possible to be used as PV
materials. In 1975, Spear et al. have accomplished the
doping of a-Si:H using boron and phosphorus to
prepare the P and N type a-Si:H thin films.5 Plasma
enhanced chemical vapour deposition (PECVD) is used
widely for preparation of a-Si:H thin films on a large
area substrate and at low substrate temperature.6–8
Adjusting the doping concentration can change effec-
tively the Fermi energy level in a large range and finally
control the electrical properties of a-Si:H thin film.
1
State Key Laboratory of Solidification Processing, Carbon/Carbon
Composites Research Center, Northwestern Polytechnical University,
Xi’an 710072, China
2
School of Materials Science and Engineering, Xi’an University of
Technology, Xi’an 710048, China
*Corresponding author, email luyuanyuan85@163.com
suffer light induced degradation, resulting in a reduction
in the power conversion efficiency of the device.9,10 The
light induced degradation is attributed to an intrinsic
phenomenon typical of the disorder network consisting
of Si and H, which forms metastable Si dangling bond
defects and acts as recombination centres for electron–
hole pairs and consequently decreases the photocarrier
lifetime. To overcome the degradation of a-Si:H thin
film, hydrogenated microcrystalline silicon thin films
(mc-Si:H) have attracted a lot of attention in recent years
due to its higher electronic properties. Crystalline silicon
thin film is a two-phase mixed material,11 consisting of
crystallites and amorphous phase.
In this paper, phosphorus and boron doped silicon
thin films have been deposited by PECVD, and their
microstructure and the electrical properties before and
after annealing have been compared. The difference
between the influence of doping gas flow ratio and the
microstructure on the electrical properties of the doped
silicon thin films has been investigated.
Experimental
Two series of phosphorus and boron doped silicon thin
films were prepared in a single-chamber PECVD system
to study their structural and electrical properties. Then,
the optimised phosphorus and boron doped silicon thin
films were annealed in vacuum at the temperature of
600uC to change their structures.
The mixture with gas flow ratios of SiH4:H257:200 (in
standard cubic centimetre per minute) were used as gas
sources. The rf power, substrate temperatures and

ß 2015 W. S. Maney & Son Ltd.

Received 15 July 2014; accepted 14 September 2014
28 DOI 10.1179/1753555714Y.0000000195 Materials Technology: Advanced Performance Materials 2015 VOL 30 NO 1

a phosphorus doped films; b boron doped films
1 Raman spectra of doped films for different flow ratios
operating pressure were kept constant at 100 W, 200uC
and 40 Pa respectively. The phosphorane (PH3) and
borane (B2H6), diluted in hydrogen to the concentration
of 15%, were used as the doping gases. Note that the
used notation of doping ratio, [PH3]/[SiH4] and [B2H6]/
[SiH4], denotes a flow ratio of pure PH3 to SiH4 and
B2H6 to SiH4. Both film series were deposited at
different flow ratios in the range from 0?5 to 2?5%.
For structural and electrical properties measurement,
HR800 Raman spectroscopy and PHI Adept 1010
secondary ion mass spectrometer (SIMS) were used for
the investigation of the microstructure and net doping
concentration of the films respectively, and the dark
conductivity, carrier concentration and mobility of the
films were measured using HMS-7077 semiconductor
characterisation system.
Results and discussion
Before annealing
Microstructure
Figure 1 shows the Raman spectra of phosphorus and
boron doped film series. A similar result has been
reported for the both series; it is that the Raman spectra
a phosphorus doped films; b boron doped films
2 Dark conductivity and carrier concentration of doping films as function of [B2H6]/[SiH4] and [PH3]/[SiH4] flow ratio
Materials Technology: Advanced Performance Materials
Lu et al. Influence of doping on doped silicon thin films
shows the peaks centred at 150 and 480 cm21 originating
from the amorphous phase, and the asymmetric band
centred at ,520 cm21 originating from the nanocrystal-
line phase12 has not been found. It indicates that the both
doped film series are amorphous in the [PH3]/[SiH4] and
[B2H6]/[SiH4] flow ratio range of 0?5–2?5%. It can be seen
that doping has not changed essentially the structure of
the doped silicon thin films in this paper.
Electrical properties
Dark conductivity and carrier concentration are the
most intuitive parameter for electrical property of the
semiconductor.13 Figure 2 shows the dark conductivity
and carrier concentration of doped films as a function of
the [PH3]/[SiH4] and [B2H6]/[SiH4] flow ratios.
For the phosphorus doped film series (Fig. 2a), there
is a sustainable improvement in the dark conductivity as
the [PH3]/[SiH4] flow ratio increases. The dark con-
ductivity increases by three times in the flow ratio range
from 0?5 to 1?5% and then tends to saturate. Differently,
the carrier concentration increases significantly as the
[PH3]/[SiH4] flow ratio increases from 0?5 to 1?5% and
then decreases obviously when the flow ratio is .1?5%.
The valence shell electron configurations of the phos-
phorus atom is (3s)2(3p)3. In gas state, phosphorus
2015 VOL 30 NO 1 29
Lu et al. Influence of doping on doped silicon thin films
atoms usually tend to bond with three coordination
silicon atoms in hybrid orbital of sp3. There are a small
number of phosphorus atoms bonding with five
coordination silicon atoms in hybrid orbital of sp3d to
form the compound with trigonal bipyramid structure.
In solid state, the compound will change to regular
tetrahedron structure from trigonal bipyramid structure
after ionising an electron. These electrons could result in
the increase in the carrier concentration. The phos-
phorus atoms as the substitutional doping have doped
into Si–Si network structure to form Si–P bond, the
density of the defect state decreases, which could
improve the dark conductivity.
For the boron doped film series (as shown in Fig. 2b),
the dark conductivity increases generally as the [B2H6]/
[SiH4] flow ratio increases except the value correspond-
ing to the [B2H6]/[SiH4] flow ratio of 1?0%, which
amount to that of 2?5%. Similarly, the carrier concen-
tration corresponding to the [B2H6]/[SiH4] flow ratio of
1?0% is up to that corresponding to the [B2H6]/[SiH4]
flow ratio of 2?5%. Owing to the disordered structure of
a-Si thin film, the atomic arrangement is not limited
strictly by topological structure so that boron atoms
may be four- or threefold coordinations. However, the
energy for threefold coordinations is lower, most of
boron atoms are threefold coordinations and minority
boron atoms are fourfold coordinations. The energy
positions of fourfold coordinations are in the scale of
band tail of a-Si, so the shallow acceptors could be
formed. As the [B2H6]/[SiH4] flow ratio increases, boron
replaces the H in Si–H bond and form the Si–B bond,
which has low electroactivity, thus decreasing the
density of defect state. Accordingly, the carrier concen-
tration and dark conductivity both increase. In addition,
impurity scattering mechanism is improved when the
[B2H6]/[SiH4] flow ratio increases further, which impacts
the carrier density and the dark conductivity.
According to the results above, varied [PH3]/[SiH4]
and [B2H6]/[SiH4] flow ratio can change the electrical
properties by one order of magnitude, and the electrical
properties for [PH3]/[SiH4] of 1?5% and [B2H6]/[SiH4] of
1?0% are equal to the electrical properties for the doping
ratios of 2?5%. This phenomenon may attribute to that
the films obtained under these conditions have same
effective doping concentration. To verify the corollary,
SIMS was used to test the net doping concentration of
the films obtained in the [PH3]/[SiH4] flow ratios of 1?5
and 2?5% and in the [B2H6]/[SiH4] flow ratios of 1?0 and
2?5%.
Secondary ion mass spectrometer
Figure 3a and b shows phosphorous and boron SIMS
profiles for the n- and p-type samples respectively. In the
figure, the X axis reflects the film thickness, and the Y
axis reflects the change of the effective doping concen-
tration with the increase in thickness. As it is shown in
Fig. 3a, the net phosphorous concentrations of the both
samples are E21 orders of magnitude. It indicates that
the net phosphorous concentration for the [PH3]/[SiH4]
flow ratio of 1?5% corresponds to that for the flow ratio
of 2?5%, which verifies the deduction in the section on
‘Electrical properties’. When [PH3]/[SiH4] flow ratio is
1?5%, the net phosphorous concentration is unchanged
throughout the whole film thickness, indicating that the
film is uniform. In comparison, the net phosphorous
concentration has changed with the film thickness as
30 Materials Technology: Advanced Performance Materials 2015
[PH3]/[SiH4] flow ratio is 2?5%. This is because, excessive
phosphorous incorporation could affect the stability of
the reaction so as to impact the uniformity of the film.
The results for the boron doped film series are the same
with the phosphorus doped film series. That is, the net
boron concentration for the [B2H6]/[SiH4] flow ratio of
1?0% is equal to that for the flow ratio of 2?5%, while the
film obtained in the [B2H6]/[SiH4] flow ratio of 1?0% is
more uniform than that obtained in the flow ratio of
2?5%. In conclusion, the performances of the films
obtained in [PH3]/[SiH4] flow ratio of 1?5% and [B2H6]/
[SiH4] flow ratio of 1?0% are superior to the films
obtained in flow ratios of 2?5%. Combining this result
with the electrical properties, it is concluded that the best
[PH3]/[SiH4] and [B2H6]/[SiH4] flow ratio is 1?5 and 1?0%
respectively.
After annealing
Microstructure
Figure 4 shows the Raman spectra of phosphorous and
boron doped films before and after annealing. As it can
be seen in Fig. 4, comparing with the films before
annealing, the bands centred at 150 and 480 cm21
originating from the amorphous phase remain appearing
after annealing; however, their strength decreases, and
the peak present a red shift because of the films become
structurally more ordered according to Raman results.
The asymmetric band centred at ,640 cm21 originating
from the amorphous phase disappears, although the
band centred at ,520 cm21 originating from the
nanocrystalline phase has been yet not found. The
results indicate that the films are not standard amor-
phous and have a tendency of transformation from
amorphous to crystalline. There should be a few micro-
or nanosize crystallites exiting in the film after annealing
although the film is not crystalline as a whole.
Electrical properties
Comparing the electrical properties of the films before
and after annealing, the values of the dark conductivity,
carrier concentration and mobility are shown in Table 1.
As shown in Table 1, the electrical properties of the films
after annealing improve obviously. For phosphorus
doped films, the dark conductivity and carrier concen-
tration increase by three and two orders of magnitude.
Similarly, the conductivity and carrier concentration of
boron doped films also increase by two and three orders
of magnitude respectively. It is can be seen that
annealing is an efficient method to improve the electrical
properties of the films.
In the annealing process, the atoms acquire enough
energy to rearrange, which improves the order degree of
the film. The doping atoms existing in the interstice of
the silicon atoms move to the lattice and form the
effective substitutional doping; thus, more carriers
generate in the film and the carrier concentration
increases. At the same time, the number of crystallites
in the film can increase at higher temperature, and the
scattering centre of carriers will decrease, which improve
the carrier mobility. The improvement of carrier
concentration and mobility can improve clearly the
dark conductivity of the film. Moreover, in the anneal-
ing process, the phenomenon of the decrease in the
defect density, the elimination of the internal stress and
the increase in compactness also improves the carrier
concentration and the dark conductivity of the film.
VOL 30 NO 1
 Lu et al. Influence of doping on doped silicon thin films

a phosphorus doped films; b boron doped films

3 Phosphorous and boron SIMS profiles for doped films

a phosphorus doped films; b boron doped films

4 Raman spectra of doped films annealed

Materials Technology: Advanced Performance Materials 2015 VOL 30 NO 1 31

Lu et al. Influence of doping on doped silicon thin films
Table 1 Dark conductivity, carrier concentration and mobility of doped films before and after annealing
Type Annealing condition Conductivity/S cm–1
N Before annealing 4.07610–5
After annealing 1.07610–2
P Before annealing 1.12610–4
After annealing 1.99610–2
Conclusion
In this work, phosphorus and boron doped silicon thin
films were deposited by PECVD, and the samples with
best doping gas flow ratios were annealed in vacuum to
change the structure. Microstructure and doping con-
centration were investigated using Raman spectroscopy
and SIMS, and the dark conductivity, carrier mobility
and concentration of the films were measured using
semiconductor characterisation system. Before anneal-
ing, all of the films are amorphous despite of the
different doping gas flow ratios, and the doping has a
weak influence on the electrical properties of the doped
films by only one order of magnitude. It is obtained that
the best flow ratios of [PH3]/[SiH4] and [B2H6]/[SiH4] are
1?5 and 1?0% respectively. After annealing, the film
expresses a tendency of transition to crystalline from
amorphous through the Raman results. The dark
conductivity and carrier concentration increases by
two to three orders of magnitude for both doping series.
It can be concluded that the structure has more influence
on the electrical properties of doped silicon thin film
than the doping concentration. Therefore, based on the
best doping ratio, the improvement of microstructure is
the key solution to improve the property of silicon based
thin film solar cells.
Acknowledgements
This work has been supported by the National Natural
Science Foundation of China under grant no. 51221001,
the ‘111’ Project under grant no. B08040 and the
National ‘973’ Project of the People’s Republic of
China under grant no. 2011CB605806.
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