Journal of Non-Crystalline Solids 358 (2012) 2035–2038

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Journal of Non-Crystalline Solids

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Time evolution of surface defect states in hydrogenated amorphous silicon studied by

photothermal and photocurrent spectroscopy and optical simulation
J. Holovský a, b,⁎, M. Schmid a, M. Stuckelberger a, M. Despeisse a, C. Ballif a, A. Poruba b, M. Vaněček b
a
Photovoltaics and Thin Film Electronics Laboratory, Institute of Micro-engineering (IMT), Ecole Polytechnique Fédérale de Lausanne (EPFL), Rue Breguet 2, 2000 Neuchâtel, Switzerland
b
Institute of Physics of the ASCR v. v. i., Cukrovarnicka 10, 162 53 Prague 6, Czech Republic

a r t i c l e i n f o a b s t r a c t

Article history: The time evolution of surface defect density and width of space charge region in thin layer of amorphous silicon
Received 17 August 2011 is observed experimentally by Fourier transform photocurrent spectroscopy. This work reviews the assumption
Received in revised form 15 November 2011 that photocurrent is insensitive to surface defects for samples thinner than 1500 nm. We show that correct eval-
Available online 30 December 2011
uation based on simple optical model comprising layers representing surface defects and layers representing
space charge region with reduced collection allows obtaining the same results as from photothermal deflection
Keywords:
Amorphous silicon;
spectroscopy. Our main approach is the comparison of photocurrent or photothermal deflection spectra mea-
Photocurrent spectroscopy; sured in absorptance/transmittance mode from layer and substrate side of the thin film.
Surface defects © 2011 Elsevier B.V. All rights reserved.

1. Introduction Time varying surface adsorption or oxidation processes were ex-

Photocurrent and photothermal deflection spectroscopy (PDS) are
methods for the characterization of material disorder and sub-
bandgap defect states in semiconductors. In the PDS method, the
total energy dissipated in the sample (and also substrate) is detected
[1]. Conversely, photocurrent spectroscopy detects only the absorp-
tance that leads to free carrier generation. The photocurrent method
is generally more complex due to the additional effect of carrier
collection that depends on defect distribution through the sample
and might depend on illumination as well. Fourier transform photo-
current spectroscopy (FTPS) [2] or constant photocurrent method
(CPM) [3] can be used for photocurrent spectroscopy of semiconduc-
tors like hydrogenated amorphous silicon (a-Si:H).
Samples of a-Si:H are usually deposited as thin layers on low
absorbing glass. Defect absorption and lifetime have typical inhomo-
geneity caused by sample free surface and/or interface with the sub-
strate [4,5]. It is well known that the excess defect absorption on a
surface can enhance modulation of interference patterns in PDS,
depending on the side of illumination incidence [6–8]. The accuracy
of the absorption coefficient calculation can be improved by removal
of the interference maxima prior to the evaluation by division of the
absorptance (A) by the transmittance (T) [9]. Then, the presence of
surface defects is indicated by residual interference maxima in the
ratio (A/T) at region of defect absorption [10]. We will show that
the residual interferences depend on the side of illumination inci-
dence with respect to defective surface.
⁎ Corresponding author at: Institute of Physics of the ASCR v. v. i., Cukrovarnicka 10,
162 53 Prague 6, Czech Republic. Tel.: + 420 220318516.
E-mail address: holovsky@fzu.cz (J. Holovský).
tensively studied by dark conductivity [11,12] that can be strongly
influenced by the surface states related band-bending that can reach
several hundred nanometer depth in the material with defect densi-
ties below 10 17 cm − 3 [13].
In photocurrent spectroscopy of a-Si:H, the surface recombination
together with the lower lifetime in the depleted region leads to a
‘dead zone’ of reduced signal at the surface. Therefore, an assumption
that photocurrent is insensitive to surface defects is adopted fre-
quently [10,14–16] and the comparison of PDS and CPM is then
used to study surface defect concentration [15,16]. However, ob-
served residual interferences in A/T ratio of photocurrent spectra
[10] still indicate that this assumption may need revision.
In this contribution, we combine a time evolution investigation
with the spectroscopic methods CPM and FTPS in the absorptance/
transmittance mode applied from both substrate and free surface
side of the sample. We analyze results by optical simulations. Our
aim is mainly motivated to correctly evaluate spectra of FTPS of thin
samples that are in our case around 350 nm thick. We show that
upon correct evaluation very similar results can be obtained for
FTPS and PDS methods.
2. Optical model
The semiconductor layer on glass is represented as a stack of mul-
tiple homogeneous thin sub-layers on thick substrate (see Fig. 1).
Transmittance and absorptance in each sub-layer is calculated by ma-
trix approach [17]. Each layer has an absorption coefficient composed
of a component representing band-to-band transitions and a compo-
nent representing defect-to-band transitions for bulk states, see
Fig. 1. Our purpose is not to investigate profiles of surface defect in

0022-3093/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jnoncrysol.2011.12.031
2036 J. Holovský et al. / Journal of Non-Crystalline Solids 358 (2012) 2035–2038
Fig. 1. Representation of different sub-layers and their components of absorption
coefficient in optical model. Defect-to-band spectra are an example of as-deposited
state as was obtained by fit of PDS measurement.
detail as in [5,7] but we show that the surface defects can be approx-
imately represented by the first and the last sub-layers of thicknesses
fixed to 1 nm that have an additional component of absorption coef-
ficient representing defect-to-band transitions for surface states. The
defect-to-band contributions are evaluated from the measured data.
Their shapes are assumed not to change shape but only magnitude
and to be different for surfaces where the Fermi level is close to con-
duction band than for bulk, where the Fermi level is close to mid-gap
[18].
In Fig. 2, we simulated the behavior of residual interferences in ab-
sorption coefficients calculated from A/T according to [9] in regions of
defect absorption of a-Si:H (around 1.2 eV) for PDS and illumination
from front side or back side, i.e. from side of the layer or substrate.
We can observe as general rule that the surface defect density on
the illuminated side increases the interference modulation. On the
other hand, the surface defect density on the side opposite to the illu-
mination creates no residual interferences but only increases the ab-
sorptance, and can to a certain extent reduce the interferences
created by the defects on the illuminated side. Also, the modulation
depth of residual interferences always decreases with increasing
bulk defect concentration. Therefore, we can like this attribute any
Fig. 2. Simulated change of residual interferences in PDS method with increase of
defect density of front surface, back surface or bulk.
changes of absorption around 1.2 eV to either bulk or surface defects
according to the change of the residual interference modulation.
The effect of lower carrier collection in FTPS due to the lower life-
time near the surfaces was represented in the optical model by the
‘dead zones’ from which the contribution to simulated absorptance
was reduced by a constant reduction factor that was obtained from
comparison of PDS and FTPS spectra. Reduction factor equal to zero
would exclude the effect of surface states and would not reflect the
experimental reality of presence of residual interferences observed
in photocurrent spectroscopy [10]. Fig. 3 shows the simulated effect
of the insertion of a 150 nm thick dead zone on one side and of two
75 nm thick dead zones on both sides in the 350 nm thick layer of
a-Si:H on the evaluation of absorption coefficient with absolute scal-
ing in high absorption. Approximately, the effect is the shift of the
whole absorption coefficient curve downwards due to effectively
thinner sample.
An exception is the case of the illumination from the back side
with the dead zone on the front side. In that case the region of medi-
um absorption is underestimated when absolutely scaled at high ab-
sorption, e.g. by additional transmittance, reflectance measurement.
From this point of view, measurement with illumination from the
dead zone side, usually layer side, is more accurate.
The difference in the spectra measured from two sides can serve
as an indication of the presence of the dead zone. However, the sym-
metrical case of equally thick dead zones on both sides, as shown also
in Fig. 3, gives results that are independent on illumination incidence.
A more precise investigation of the simulated curves also in re-
gions of medium or low absorption shows that not only the shift
but also the shape is changed by the presence of dead zones. To con-
clude, simulation of dead zones demonstrates their effect on whole
spectrum. However all these effects are generally weaker for thicker
samples.
3. Experiment
The 360 nm thick layer of intrinsic a-Si:H was deposited on a low
alkaline glass by VHF PE-CVD from silane diluted by hydrogen at
50 Pa and substrate temperature 200 °C. One part of the sample was
characterized by PDS (with use of CCl4) and the other part was char-
acterized by FTPS (coplanar Al contacts, spacing 1 mm, 300 V bias).
Absorptance and transmittance were measured from both sides of
the samples by both techniques. The first measurement was taken
on the day of the deposition and the measurement was later repeated
Fig. 3. Simulated change of calculated absorption coefficient as determined by FTPS
with absolute scaling at high absorption (e.g. by T,R) with incorporation of one or
two dead zones. Lower set of spectra are divided by 10.
 J. Holovský et al. / Journal of Non-Crystalline Solids 358 (2012) 2035–2038 2037

several times. Samples were stored on air in dark. As a last step, the
samples were degraded by light soaking from layer side for 400 h
under roughly 1 sun at 50 °C.
The evaluation proceeded in several steps: 1) The absorption coef-
ficient of band-to-band transitions was obtained from A/T spectra
measured by PDS above 1.5 eV, where no effect of surface states oc-
curs. Absolute scaling of A/T together with Cauchy parameters of re-
fraction index and thickness were obtained from numerical fit [10].
The exponential part of the absorption edge was extended below
1.5 eV to remove effects of any defect states, see Fig. 1. 2) The spectra
of bulk defect absorption were fitted from light soaked curves of PDS,
where contribution of surface states was small and without the effect
of dead zones. 3) The spectra of surface states were fitted from the
PDS data of as deposited sample for which the effect is the strongest.
4) Relative magnitudes of spectra of defect states were evaluated for
spectra of all other measurements followed in time series. Such rela-
tive magnitudes were calculated also for FTPS data but the dead zone Fig. 5. FTPS spectra in A/T regime and numerical fit accomplished by changing magni-
tudes of surface and bulk defect absorptance and the thickness of dead zone. The spec-
reduction factor was adjusted at the same time in order to obtain the
tra are normalized at 1.7 eV and shifted mutually by a factor 1/10.
same absolute values of surface defect states for FTPS as for PDS. Since
the FTPS spectra are just relative, the normalization was done at
1.7 eV. 5) Once the reduction factor was known, the thickness of accuracy. The last light soaking step affected almost exclusively the
dead zone was fitted at the medium to high absorption region. The bulk defect density except for the dead zone thickness that dropped
dead zone present only on the front surface (exposed to air) was significantly. The agreement between bulk defect concentration
assumed. At the end, the steps 2–5 were repeated several times to it- obtained from PDS and FTPS gives also confirmation to our method.
eratively increase accuracy of the fit. Experimental and fitted PDS and For the obtained parameters we assessed in accordance with [19]
FTPS spectra can be seen in Figs. 4 and 5. that the photocurrent in as deposited state would be practically in-
sensitive to surface defects if sample thickness was more than
4. Results 1.5 μm. For PDS, this threshold would be even four times higher.

Fig. 6 summarizes how the bulk and surface defect densities chan- 5. Discussion
ged in time. The fitted value of the reduction factor in dead zone is ¼.
Values in Fig. 6 are ‘true’ material input values for optical model and In the calculation of defect densities we used twice higher factor
might be rather different from ‘apparent’ values obtained by standard for FTPS than that for PDS, same value as for CPM [19]. The explana-
evaluation methods, e.g. with neglecting the dead zone. The fitted tion of this approximate factor 2 is that photocurrent measures only
bulk defect-to-band absorption spectra (as in Fig. 1) were trans- the occupied defect states. Based on this explanation we assumed
formed into defect density by taking the value at 1.2 eV multiplied here that all the surface defects are occupied due to the band-
by factor 2⋅10 16 cm − 2 or 4⋅10 16 cm − 2 for PDS or FTPS, respectively
[19]. For the surface defect-to-band absorption spectra the fixed
thickness 10 − 7 cm of the surface defect layers was taken into ac-
count, giving the recalculation value for surface defect density
2⋅10 9 cm − 1. This value was assumed to be equal for PDS and FTPS.
High initial value of front surface defects and a close to exponential
decrease with time is observed that can point to the effects of surface
chemical adsorption or oxidation. Defects on bottom silicon-glass sur-
face that is protected from atmosphere remained small or negligible
and almost constant. Bulk defects also stayed constant within the

Fig. 4. PDS spectra divided by transmittance and their numerical fit accomplished by

changing magnitudes of surface and bulk defect absorptance. The spectra in as depos- Fig. 6. Fitted ‘true’ material parameters as evolved with time after deposition and the
ited state are in scale, the others are shifted by a factor 1/10. light soaking for 400 h in the last step.
2038 J. Holovský et al. / Journal of Non-Crystalline Solids 358 (2012) 2035–2038
bending and give, apart from the dead zone factor, same absorptance
in PDS as in FTPS.
We can see in Fig. 6 that the thickness of dead zone has the same
trend as the concentration of surface defects, however the thickness
does not fall that fast. The significant shrinkage of the dead zone
was observed only after the light soaking. This can be explained e.g.
by the fact that depletion layer depth depends on defect density
[13]. However as surface conditions were not well defined, detailed
explanation of surface processes would be difficult and out of scope
of this paper.
6. Conclusion
Simple optical simulation was used to address the surface defects
in the Fourier transform photocurrent spectroscopy of 360 nm thick
layer of amorphous silicon on glass. Upon correct evaluation the
same results as from photothermal deflection spectroscopy were
obtained. Evaluation comprised also fit of the two different spectra
of surface and bulk defect-to-band absorption and a fit of factor that
reduces the carrier collection in space charge region. Time evolution
of magnitude of surface defect-to-band absorption as well as thick-
ness of space charge region was observed. At the same time the eval-
uated value o bulk defect density gave constant value that changed
only after light-soaking step. As a result, the commonly used assump-
tion of insensitivity of photocurrent to surface states was reviewed
and limited to samples thicker than 1500 nm. For thinner samples
the presented method based on comparison of spectra of absorp-
tance/transmittance measured from both sides of sample can be
used. Measurement from layer side was found to be safer due to the
indication of surface defect absorption by non-vanishing interference
maxima in absrorptance/transmittance mode.
Acknowledgment
This work was supported by the Swiss Federal Office of Energy
(OFEN), grant no. 101191, and by the 7th Framework program project
N2P no. CP-IP-214134 supplemented by Czech Ministry of education
support no. 7E09057.
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