Thin Solid Films 519 (2011) 45164518

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Thin Solid Films

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / t s f

Aluminum doped silicon carbide thin lms prepared by hot-wire CVD: Inuence of
the substrate temperature on material properties
Tao Chen a,b,, Deren Yang b, Reinhard Carius a, Friedhelm Finger a
a
b

IEK5-Photovoltaik, Forschungszentrum Jlich, Jlich 52425, Germany

State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou 310027, China

a r t i c l e

i n f o

Available online 2 February 2011

Keywords:
Silicon carbide
Microcrystalline
Al-doping
p-type
Thin lm
Hot-Wire CVD

a b s t r a c t
Successful p-type doping of c-SiC:H with Al introduced from trimethylaluminum has been already
demonstrated. In this work we focus on the inuence of substrate temperature (TS = 300390 C) on the Aldoping. As TS is reduced from 390 C to 300 C, the crystallinity decreases from 75% to 55% and the dark
conductivity D decreases rst by about three orders of magnitude before increasing again at TS = 300 C. Both
microstructure, as determined from Raman spectroscopy, and optical absorption are little affected by the change
in TS. Upon annealing at 450 C in vacuum, D increases typically by two orders of magnitude up to 104 S/cm,
which is explained by dopant activation as a result of hydrogen desorption. It is concluded that a process
temperature N 350 C is needed to obtain effective Al-doping for p-type c-SiC:H thin lms.
2011 Elsevier B.V. All rights reserved.

1. Introduction
Highly crystalline cubic-like microcrystalline silicon carbide
(c-SiC:H) thin lms prepared by Hot-Wire Chemical Vapor Deposition
(HWCVD) technique at low substrate temperatures (b300 C) have been
already reported [13]. These c-SiC:H thin lms are highly transparent
and n-type conductive. It is proposed that impurities like nitrogen and/or
oxygen could be the possible dopants [4,5]. Such n-type c-SiC:H
window layers have been successfully applied in microcrystalline silicon
(c-Si:H) thin lm solar cells [4,6] and silicon heterojunction solar
cells [1,7]. Stimulated by the success of n-type c-SiC:H window layers,
p-type c-SiC:H window layers are now investigated for the application
in a-Si:H or a-Si:H/c-Si:H tandem solar cells. Only recently, the
preparation of p-type c-SiC:H thin lms doped by Aluminum (Al) in
the HWCVD process has been realized [810]. According to annealing
studies [10,11], a substrate temperature of above 350 C was reported to
prevent the Al acceptor from being passivated by hydrogen [12]. So far
no direct investigation of the inuence of substrate temperature on the
Al-doped c-SiC:H thin lms has been reported. In this study, the
material properties of Al-doped c-SiC:H thin lms deposited at various
substrate temperatures will be addressed.

Rhenium laments were used. The lament temperature was about

2000 C, which is measured by a two-color pyrometer. A gas mixture of
monomethylsilane (MMS) diluted in hydrogen with a concentration
of 0.6% was used as the SiC source. Trimethyaluminum (TMAl) was the
Al-doping source, which was introduced into the deposition process by
a bubbler system. By controlling the thermo-bath temperature, the
bubbler pressure, and the ow rate of carrier gas H2 in the bubbler
system, the TMAl/MMS ow rate ratio (rdoping) was xed at 3.1%. The
substrate temperature (TS) was varied in a range of 300390 C by
adjusting the heater temperature. A single color pyrometer was used to
monitor TS during the deposition process. The TS shown in this study is
the stabilized value during the deposition. Other deposition parameters
like the total ow rate, the deposition pressure, and the deposition time
were 100 sccm, 75 Pa, and 120 min, respectively. The Al-doped c-SiC:H
thin lms were deposited on glass (Corning 1737) for dark conductivity
and photothermal deection spectroscopy (PDS), on glass coated with
chromium (Cr) grids for Raman spectroscopy, and on Si wafer for
Infrared spectroscopy. The dark conductivity was measured in vacuum
at room temperature. Raman measurements were carried out using
488 nm laser line of an Argon laser for excitation. A commercial Fourier
transform infrared spectrometer was used for the infrared absorption
measurement.

2. Experimental details
3. Results
c-SiC:H thin lms doped by Aluminum were deposited in a single
chamber HWCVD system with a load-lock. Three pieces of coiled
Corresponding author at: IEK5-Photovoltaik, Forschungszentrum Jlich, Jlich
52425, Germany.
E-mail address: t.chen@fz-juelich.de (T. Chen).
0040-6090/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2011.01.298

Fig. 1 shows the deposition rate of Al-doped c-SiC:H thin lm

prepared as a function of substrate temperature (TS). The lm thickness
measured by a step proler is in the range of 250320 nm. The
deposition rate is 0.4 /s at 300 C and decreases to 0.34 /s when TS
increases to 390 C. The reason for this decrease is not understood. The

T. Chen et al. / Thin Solid Films 519 (2011) 45164518

4517

0.44

Infarared crystallinity fL-G

Deposition rate rd (/s)

0.8
0.42
0.40
0.38
0.36
0.34
0.32
0.30

0.7

0.6

0.5

300

320

340

360

380

300 310 320 330 340 350 360 370 380 390

400

Substrate temperature TS (C)

Substrate temperature TS (C)

Fig. 1. The deposition rate of Al-doped c-SiC:H thin lms as a function of the substrate
temperature (TS). The dashed line is a guide to the eye.

Fig. 3. The dependence of the infrared crystallinity (fLG) of Al-doped c-SiC:H thin lms
on the substrate temperature (TS). The dashed line is a guide to the eye.

increase of substrate temperature will likely lead to a decrease of

hydrogen coverage at the surface of the growing lm. In this case an
increase of deposition rate would be expected, which is different from
what we observe here. The structural properties of these Al-doped cSiC:H thin lms were studied by Raman and Infrared measurements.
The Raman spectra of these samples are shown in Fig. 2. Very alike
Raman features are observed in all spectra with three peak bands: 400
600 cm1, 770800 cm1, and 890960 cm1. These bands can be
assigned to the acoustic modes (TA/LA), the transverse optical (TO) and
the longitudinal optical (LO) modes of silicon carbide, respectively. The
broad bands in the spectra are due to the overlapping Raman signals of
different SiC polytype like cubic or hexagonal [13,14]. Taking the band at
890960 cm1 for example, two peaks at about 890 and 960 cm1
could be deconvoluted. The peak at 890 cm1 can originate from the LO
modes of stacking faults or hexagonal phase in SiC, which is
accompanied by the TO modes at about 760 cm1 [14]. The peak at
960 cm1 can be attributed to the LO mode of cubic SiC polytype with
the corresponding TO mode at about 790 cm1 [14,15]. Similar Raman
spectra were observed in our previous study on Al-doping of c-SiC:H
thin lms [10]. Indicated by the very similar Raman features in all
samples, the microstructure of these Al-doped c-SiC:H samples varies
little with increasing TS.
Due to the varieties of SiC polytype, the evaluation of crystalline
volume fraction from Raman spectra of c-SiC:H thin lms is
obstructed. Instead, the ratio of Lorentzian-to-Gaussian contribution
(fLG) in the infrared absorption line of SiC stretching mode is used to
qualitatively demonstrate the variation of crystallinity [5,10], as

shown in Fig. 3. The value of fLG increases by about 20% when TS

increases from 300 C to 390 C, indicating the increases of crystallinity of the Al-doped c-SiC:H thin lms.
Fig. 4 shows the dark conductivity of the Al-doped c-SiC:H thin
lms deposited at different TS. At TS = 300 C, the conductivity is about
108 S/cm. It initially decreases by about one order of magnitude as TS
increases to 320 C, and then increases up to 106 S/cm at TS = 390 C.
After annealing at 450 C in vacuum for 30 min, the dark conductivity
of most samples increases to about 104 S/cm, except for the sample
with TS = 320 C where the conductivity only increases to a few times
of 107 S/cm. It is still under investigation in how far this trend in
conductivity versus TS and the annealing temperature for the samples
prepared at the low TS (300320 C) is reproducible. At present, we
can only speculate on explanations (see Discussion). Generally it can
be said that similar high conductivities are obtained, no matter how
the highest temperature in the sample history is: during deposition or
after annealing. This effect can be attributed to a reduction in the number
of passivating AlH complexes at higher temperatures [8,11,16].
Finally the optical absorption coefcient of these c-SiC:H samples
measured by PDS is shown in Fig. 5. The optical band gap E04, which is
dened by the photon energy where the optical absorption coefcient is
104 cm1, is about 2.5 eV and very similar for all TS except for the sample
prepared at TS = 300 C where a slightly lower gap is indicated. The subgap absorption, e.g. at h = 0.7 eV, is about 102 cm1 for the samples

SiC
TO

Raman intensity (a.u.)

SiC
LA/TA

SiC
LO

TS

Dark conductivity D (S/cm)

1E-3

c MMS = 0.6% (100 sccm), rdoping = 3.1%, pdepo = 75 Pa, TF = 2000 C

1E-4
1E-5
1E-6
1E-7
1E-8
1E-9

Cr
1E-10

As deposited
Annealed at 450 C for 30 min

300 310 320 330 340 350 360 370 380 390
400 500 600 700 800 900 1000 1100 1200 1300 1400

Raman shift (cm-1)

Fig. 2. The Raman spectra of Al-doped c-SiC:H thin lms prepared at various substrate
temperature (TS).

Substrate temperature TS (C)

Fig. 4. The dark conductivities of Al-doped c-SiC:H thin lms as a function of the
substrate temperature (TS). The open circle: samples at as-deposited state; the solid
circle: samples after annealed at 450 C in vacuum for 30 min. The dashed line is a guide
to the eye.

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T. Chen et al. / Thin Solid Films 519 (2011) 45164518

while the dissociation energy of the AlH complex is not reached in this
TS range. After TS is increased above 320 C, the AlH complex becomes
unstable, and the Al acceptors begin to get activated. Therefore, the dark
conductivity increases when increasing TS N 320 C. The sub-gap
absorption obtained from PDS for the as-deposited material follows at
least qualitatively the trend which would be expected from the
conductivities (Fig. 4) if we contribute this absorption to free carriers
i.e. the highest sub-gap absorption is obtained for the lms prepared at
300, 365 and 395 C. But additional contributions from defect can also
not be excluded here, especially at higher TS.

105

104

103

TS = 300 C
TS = 320 C
TS = 330 C

102

TS = 345 C
TS = 365 C
TS = 395 C

10

5. Conclusions

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

Fig. 5. The PDS spectra of Al-doped c-SiC:H thin lms prepared at various substrate
temperatures (TS).

prepared at TS = 300 C, 365 C and 395 C. For the intermediate TS

(320365 C) the absorption coefcient is signicantly lower.
As a summary, the dark conductivity rstly decreases from 108 S/cm
to below 109 S/cm when TS increases from 300 C to 320 C. As TS
increases further, the dark conductivity increases to 106 S/cm at
TS = 390 C. The study of annealing at 450 C indicates that the samples
prepared at higher TS (TS N 350 C) show less difference in dark
conductivity before and after annealing. According to the Raman result,
the microstructure of these Al-doped c-SiC:H materials is mainly SiC
with cubic and hexagonal structures, and varies little within the
investigated TS range. Infrared absorption indicates an increasing
crystallinity with increasing TS. The band gap does not change
signicantly but the sub-gap absorption exhibit a pronounced minimum
at intermediate substrate temperatures.
4. Discussion
The increase of substrate temperature in the HWCVD preparation of
c-SiC:H leads to an increase in crystallinity and via its inuence on
hydrogen desorption during the growth process affects the electronic
properties of the Al-doped material considerably. The hydrogen atoms
in the growing lm are forming SiH or CH bonds and are
saturating the dangling bonds, or deactivating the Al acceptors by
forming an AlH complex [12,16]. Different energies are required to
break these bonds or H containing complexes. From the annealing
studies of Al-doped c-SiC:H thin lms deposited at TS 300 C one can
conclude that the AlH complex is broken up when the annealing
temperature is above 400 C [11]. This will result in a more effective
doping and higher conductivity as observed. It is possible that in the
deposition process lower substrate temperatures might be sufcient for
the de-passivation of Al acceptors due to the additional energy impact
from ions and radicals on the growing lm surface. Surprisingly the dark
conductivity rstly decreases by more than one order of magnitude as TS
increases from 300 C to 320 C. This could be explained by enhanced
passivation of Al acceptors as hydrogen desorption from weak bonds
like saturated dangling bonds already starts at these low temperatures,

The inuence of substrate temperature (TS = 300390 C) on the

material properties of Al-doped c-SiC:H thin lms was investigated.
It is shown by the Infrared results that the increase of substrate
temperature leads to the increase of lm crystallinity, while the
microstructure varies little as indicated by the Raman spectra. The Aldoping in c-SiC:H thin lms is strongly affected by the hydrogen
atoms. In order to obtain effective Al-doping in the as-deposited state,
TS higher than 350 C could be of advantage, while alternatively a
post-deposition annealing step seems to serve the same purpose.
Acknowledgements
We thank J. Klomfass, F. Khler, M. Hlsbeck, C. Sellmer, T. Bronger,
J. Wolff, and A. Schmalen for their contributions to this work and
U. Rau for continuous support and encouragement. The partial nancial
support from the Bundesministerium fr Umwelt, Naturschutz und
Reaktorsicherheit (Contract No. 0329986) is acknowledged.
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