Journal of Physics and Chemistry of Solids 105 (2017) 90–98

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Journal of Physics and Chemistry of Solids

journal homepage: www.elsevier.com/locate/jpcs

Nanocrystalline silicon thin films from SiH4 plasma diluted by H2 and He in MARK
RF-PECVD
⁎
Subhashis Samanta, Debajyoti Das
Nano-Science Group, Energy Research Unit, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032, India

A R T I C L E I N F O A BS T RAC T

Keywords: Systematic changes in structural, optical and electrical properties of nanocrystalline silicon (nc-Si:H) films
Nanocrystalline silicon prepared at 250 °C in capacitively-coupled RF-PECVD operated at 200 W of RF (13.56 MHz) power have been
RF-PECVD investigated as an effect of gas pressure variation in SiH4 plasma diluted by equal amount of H2 and He.
< 220 > crystallographic orientation Considering nanocrystallites with < 220 > crystallographic orientation arising due to thermodynamically
Raman scattering
preferred grain growth, an optimum pressure, p~0.6 Torr has been identified at which the maximum ultra-
Infrared absorption spectroscopy
Electron microscopy
nanocrystalline component fraction of crystallinity in the network with corresponding silicon di-hydride
components mostly in clusters control the growth. The H2-dilution in the plasma maintains a good crystallinity
while enhancement of secondary electron emission coefficient induced by He-ions has been attributed to
contribute a high growth-rate. The Si:H films at the onset of nanocrystallinity prepared at a high deposition rate
in the SiH4-depleted plasma condition at p~1.5 Torr, appears promising in the fabrication of efficient solar-
cells.

1. Introduction
Silicon based technologies are well recognised for the fabrication of
high-performance electronic devices. Nano-crystalline Silicon (nc-
Si:H) is a mixed-phase material consisting of Si nano-crystals bound
in amorphous tissue with the grain boundaries acting as potential
barriers for the carriers [1–3]. The nc-Si:H films have potential
applications in optoelectronic devices, such as thin film transistors,
solar cells as well as non-volatile memories [4–10]. The study of nc-
Si:H films is interesting because the size of the crystals and their
volume fraction affect the properties of films and their specific
orientation may appear useful for some particular device applications.
The nc-Si:H films are promising for the next generation of high efficient
thin film solar cells because of their high electrical conductivity by
virtue of high charge-carrier mobility, high stability against light
induced degradation, their improved longer wavelength response and
the tuneability of their optical band gap by controlling the grain size of
nanocrystals [11,12]. Among several deposition techniques available to
develop nc-Si:H thin films, the 13.56 MHz frequency RF plasma
enhanced chemical vapour deposition (RF-PECVD) of SiH4 and H2
mixtures has been established as the most useful one for developing
large area thin film devices on low cost substrates such as glass, steel,
or polymer, even for industrial applications [13,14].
Towards optimizing and utilizing nc-Si:H films in the fabrication of
devices a few key challenges generally exist. To realize the efficient
growth of the material at relatively low temperature on large surface
area and with high deposition rate are the requirement of its cost
effective utilization by the industry. Further, specific growth of the
nanocrystallites e.g., towards (220) crystallographic orientation ap-
pears beneficial for stacked layer devices like solar cells. In general, a
high H2-dilution to the SiH4 plasma appears to be an useful parameter
for attaining improved crystallinity in nc-Si:H [13]. Recent studies with
different plasma reactors and various plasma parameters including
diverse excitation frequencies for plasma ignition strongly suggest that
the amorphous to nanocrystalline phase transition is governed kineti-
cally by the arrival rate of atomic H relative to that of the SiHn growth
precursors in the plasma [15,16]. However, high H2-dilution signifi-
cantly retards the film growth rate and stands against its commercial
viability. In this respect noble gas dilution of SiH4, e.g. with Ar, He, Xe,
Ne and Kr, has been identified as an alternative way to produce high
density plasma even at low electrical excitation and to increase the
deposition rate [17,18]. However, samples prepared with Ar dilution
are predominantly amorphous and demonstrate columnar growth
characteristics, and Xe dilution generally causes surface damage [19].
He-plasma exposure exhibits similar role as that of atomic hydrogen
exposure to initiate crystallization in a Si network. Moreover, an
enhanced deposition rate at relatively low substrate temperature and
RF power in the case of helium dilution has been attributed to the

⁎
Corresponding author.
E-mail address: erdd@iacs.res.in (D. Das).

http://dx.doi.org/10.1016/j.jpcs.2017.02.013
Received 25 November 2016; Received in revised form 20 January 2017; Accepted 13 February 2017
Available online 27 February 2017
0022-3697/ © 2017 Elsevier Ltd. All rights reserved.
S. Samanta, D. Das
enhancement of secondary electron emission coefficient induced by He
ions [20–22]. The defects and disorders still remaining in the network
could further be eliminated by the addition of small amounts of H2 into
the moderately He-diluted SiH4 plasma, where H2 plays a role to
encourage crystalline features of the films and He serves as a primary
diluent to increase deposition rate [23,24]. Increasing RF power
applied to dissociate the SiH4 molecules in the reactor is another
critical parameter which favors a higher growth rate by raising the
density of the growth precursors, and simultaneously facilitates
nanocrystallization by increasing the atomic hydrogen density in the
plasma. However, higher RF power causes surface damage by high-
energy ion bombardment which makes the process unfavorable for
device fabrication. Suppression of ion energy is crucial in improving the
crystallinity particularly at higher growth rates [25]. The ion density in
the plasma is determined by the electron density, whereas the kinetic
energy of the ions is determined by the electron temperature. Using a
particular excitation frequency in a reactor of particular geometric
configuration and electrode separation, the ion energy exerted on the
growing surface of the films could be minimized by reducing the mean
free path of the precursors in a dense plasma produced at a relatively
high gas pressure in the reactor, which in turn could facilitate
increasing the growth rate, in particular. However, particle formation
in the plasma is an obvious consequence that restricts its usability in
device fabrication [26,27]. An improvement on the electronic proper-
ties of the polymorphous silicon (pm-Si) films was revealed with an
optimum in the pressure range of 0.8–1.6 Torr, depending on tem-
perature, dilution, RF power, etc., i.e., on how fast powder forms in the
reactor [28]. It has been identified that the powder formation enhances
by the product between the inter-electrode distance and the residence
time of the SiHn precursors in the reactor. By reducing the inter-
electrode distance, the powder formation has been minimized by
effectively promoting surface reactions on the electrode instead of
volume reactions in the plasma [29]. Keeping all these in consideration,
the present investigation deals with the optimization in the growth of
nc-Si:H films by systematic variation of gas pressure in the SiH4
plasma diluted by a combination of H2 and He, at moderate RF power
and substrate temperature. An increased growth rate is expected by
virtue of He-dilution at elevated gas pressure in the plasma, H2-
dilution remains effective in maintaining the nanocrystallinity even at a
low RF power and low substrate temperature; simultaneously, refrain-
ing the plasma together from particle formation even at a sufficiently
high gas pressure in the reactor with the optimum separation of its
parallel plate capacitor electrodes. Maintaining tiny size of the nano-
crystallites with (220) oriented growth direction for facilitating device
applications are also looked into, in course of the optimization of the
parameters.
2. Experimental
Intrinsic Si:H thin films were deposited by capacitively coupled RF-
PECVD reactor of cylindrical shape with 30 cm diameter and 20 cm
height, operated at 200 W of RF (13.56 MHz) power applied to the
lower disc of parallel plate circular electrodes of 20 cm diameter placed
at an inter electrode separation of 2 cm. The electrodes were placed in
horizontal configuration. The lower electrode was simultaneously used
as the gas shower and the upper electrode held the substrates with
surface of the growing films facing downwards and heated externally
from the back. A dense plasma produced by only 0.5 sccm of SiH4 as
the precursor gas and H2 and He each of 25 sccm as the diluent gases.
Films were grown on Corning® Eagle 2000TM glass and silicon < 100 >
wafer and the carbon coated Cu microscope grids as the substrates
maintained at 250 °C temperature. A set of films were prepared by
systematically varying the gas pressure in the plasma from 0.3 to
1.5 Torr, by throttling the gas flow at the outlet of the reactor. The
thickness of the films, typically around 500 nm, was measured by
Dektak 6 M profilometer. Samples were characterized by X-ray diffrac-
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Journal of Physics and Chemistry of Solids 105 (2017) 90–98
tion analysis using a conventional Cu-Kα X-ray radiation of λ=1.5418 Å
as a source and a Bragg diffraction setup (Seifert 3000P). The optical
density data of the films (1.5×1.5 cm−2 area) were obtained using a
Hitachi 330 double-beam spectrophotometer. Electrical conductivity
measurements were performed by a Keithley 6517A electrometer and
by applying dc voltage within the Ohmic resistance region on films
(1×1 cm−2 area) prepared on glass substrates, using a coplanar Al
electrode (3 mm separation) configuration at room temperature, in a
high vacuum of ~10−6 Torr. Electrodes were deposited on the samples
by thermal evaporation after attaining a background vacuum of
~10−6 Torr. Photoconductivity of the samples were measured at room
temperature under AM1 while light illumination by a tungsten halogen
lamp. Raman backscattering measurement was performed using a
Renishaw inVia Raman Microscope with excitation wavelength of
514 nm from air-cooled Ar+ laser source operating at a low power
density ~2 mW cm−2. The silicon hydrogen bonding structure of the
films was investigated by a FTIR spectrometer (Nicolet Magna-IR 750).
Spectroscopic ellipsometry was carried out using spectroscopic ellips-
ometer (JobinYvon, Horiba) operating at a fixed angle of incidence.
High-resolution transmission electron microscopy was done by JEOL-
JSM 2010 transmission electron microscope operating at 200 kV.
3. Results
A set of nc-Si:H films were prepared by changing the working gas
pressure (p), in the range 0.3–1.5 Torr, of the SiH4 plasma diluted by
equal amount of H2 and He with a gross dilution ration, D ~99%, as
shown in detail in Table 1, and characterized by various structural,
optical and electrical studies.
The deposition rate (Rd) of the films increased very rapidly from
~10 nm/min to 16.5 nm/min for increasing p from 0.3 to 1.0 Torr
above which, however, a shallow saturation was attained in the growth
process and Rd ~18.3 nm/min was obtained at p=1.5 Torr, from a very
low flow rate (0.5 sccm) of the feedstock (SiH4), as shown in Fig. 1.
Gradual changes in the crystalline nature of Si–Si bond toward
amorphous dominated network were investigated by Raman studies.
Fig. 2(a) shows the normalized Raman spectra of the set of nc-Si:H
films. In general, each spectrum reveals asymmetric sharp peak at
~520 cm−1 corresponding to the crystalline silicon (c-Si) phase, along
with its elongated tail towards lower wave-number as the signature of a
fraction of accompanying amorphous component (a-Si) in the network.
In practice, each spectrum can be deconvoluted into three Gaussian
components; the section on the higher frequency side represents the
nanocrystalline part of the material (nc-Si) and the lower frequency
section at around 480 cm−1 is assigned to a-Si, while the intermediate
one at around 510 cm−1 corresponds to unc-Si, the ultra-nanocrystal-
line and/or the grain boundary component [30]. Because of the
presence of the Si-ncs of a wide range of diameters and the variation
of their average size in different sample, a gross shift in the peak
position of the envelop spectrum has been noted in Fig. 2(a). The
deconvolution of the individual components of the Raman spectrum for
Table 1
Deposition parameters for growing nc-Si:H films by RF-PECVD.
Substrate temperature, Ts (∘C) 250
RF power, P (W) 200
SiH4 (sccm) 0.5
He (sccm) 25.0
H2 (sccm) 25.0
D [(H2+He)/(SiH4+H2+He)] (%) 99
Deposition pressure, p (Torr) 0.3–1.5
Background vacuum level of the reactor (Torr) 1.0×10−6
Deposition time (min) 30–50
S. Samanta, D. Das
Fig. 1. Variation of the deposition rate of nc-Si:H thin films with changes of gas
pressures (p) in the plasma.
three typical samples prepared at p=0.3, 0.6 and 1.5 Torr are presented
in Fig. 2(b). The deconvoluted nc-Si components for the set of samples
have been found to systematically shift towards a lower wave number
from which the average grain size of the Si nano-crystals has been
Fig. 2. (a). Normalized Raman spectra of nc-Si:H thin films deposited at different pressures (p). (b) The deconvolution of the Raman spectrum into three satellite components for three
typical samples prepared at p=0.3, 0.6 and 1.5 Torr. (c) The variation of crystalline volume fraction, mean crystal size and relative strength of ultra nanocrystalline component at
different process pressures.
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Journal of Physics and Chemistry of Solids 105 (2017) 90–98
estimated in each case following relation [31–33]:
⎛ Γ ⎞2 ⎛ 1 ⎞ 2
(ωL − ω0 )2 + ⎜ 0 ⎟ ≅ ⎜ ⎟ × e−(π )
⎝2⎠ ⎝ 3L ⎠
where ω0 is the natural frequency and Γ0 is the natural line width of c-Si
which are 520 and 3.5 cm−1, respectively and ωL is the frequency of the
nc-Si mode of size L.
A gradual reduction in the size of the Si-ncs from ~15.6 nm to
~4.2 nm has been identified for systematic increase of p from 0.3 to
1.5 Torr, as plotted in Fig. 2(c). The gross crystalline volume fraction
XC has been estimated considering the intermediate ultra-nanocrystal-
line component as the part and portion of crystallinity and calculated
following equation [34,35]:
I520 + I510
Xc =
I520 + I510 + I480
where Ii is the integrated area under the corresponding deconvoluted
satellite component with peak centred at i. On increase in p the
crystalline volume fraction reduced systematically from ~80 to ~51.6%;
however, the unc-Si component in the network has been found to have
its maximum contribution corresponding to sample prepared at
p=0.6 Torr, as demonstrated in Fig. 2(c).
Variations in the nature of crystallinity in terms of different
crystallographic orientations were investigated by X-ray diffraction
studies. Three most dominant peaks corresponding to the (111), (220)
S. Samanta, D. Das
Fig. 3. (a) XRD spectra of nc-Si:H films prepared at different pressures. (b) The variation in grain size of Si-ncs of < 220 > and < 111 > orientation and the relative changes in
corresponding peak intensities, I < 220 > / I < 111 > , on increasing gas pressure.
and (311) crystallographic orientations of c-Si, at 2θ=28.3°, 47.2° and
56.2°, respectively, were identified in sample prepared at p=0.3 Torr.
Fig. 3(a) demonstrates that with increase in p the < 311 > peak
disappeared while the < 220 > peak became relatively sharp and
intense. However, at p above 1 Torr the overall crystallinity gradually
turned weak and went beyond the XRD detection limit. Considering <
220 > and < 111 > as the two commonly available crystallographic
features of this current set of samples, changes in their intensity ratio, I
< 220 > /I < 111 > , has been estimated and plotted in Fig. 3(b). The
average grain size (d), as estimated from the FWHM (β) of each
individual peak in the XRD spectra has also been estimated, using
Scherer's formula:
d =0. 9λ /β cosθ ,
and plotted in Fig. 3(b). The size of the Si-ncs of (111) orientation, d <
111 > , reduced monotonically on increasing p, however, that of (220)
orientation, d < 220 > , demonstrated a maximum in its magnitude at
around p=0.6 Torr which has been markedly noted to correspond to
the associated similar maximum of the intensity ratio, I < 220 > /I < 111 > .
Investigation on the changes in different bonding configurations
between Si and H was pursued by infrared absorption spectroscopy.
The absorption spectra of the films identify major absorption peaks
mainly in three different spectral ranges around 540–750 cm−1, 800–
950 cm−1 and 1900–2200 cm−1. The spectra in Fig. 4(a), around 540–
750 cm−1 can be deconvoluted into two well resolved peaks centred at
~630 cm−1 and 670 cm−1, corresponding to the Si–H wagging and SiHn
(n≥2) rocking modes of vibration, respectively. The bonded hydrogen
content (CH) in each network has been estimated from the integrated
absorption of the Si-H wagging mode component at 630 cm−1, follow-
ing [36]:
CH = (A ω / NSi ) ∫ αd ω/ω × 100 at%,
where Aω=1.6×1019 cm–2 is the wagging mode oscillator strength and
NSi=5×1022 cm–3 is the c-Si atomic density. The proportional inte-
grated intensity of the SiHn (n≥2) rocking mode absorption compo-
nent,
ΔI 670 = I 670 / (I 630 + I 670)
basically presents the relative strength of the polyhydride component
in the network. The nature of variations in the magnitude of CH and
ΔI670 plotted in Fig. 4(b) demonstrate a sharply increased bonded H-
content along with simultaneous gross reduction in poly-hydrogenation
of the network at increased gas pressure in the plasma, p≥1.0 Torr.
Furthermore, the deconvolution of the spectra in the range, 800–
950 cm−1 identify two components: the (SiH2)n poly-hydride wagging
complex and isolated SiH2 di-hydrides at 850 and 895 cm−1, respec-
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Journal of Physics and Chemistry of Solids 105 (2017) 90–98
tively, shown in Fig. 4(c) [37]. The relative strength of the (SiH2)n poly-
hydride wagging complex plotted in Fig. 4(d) identifies its maximum
intensity at around 0.6–0.8 Torr above which the network becomes less
poly-hydrogenated, although overall bonded H-content increases.
The absorption band around 1900–2200 cm−1 identified three
satellite components corresponding to the monohydride SiH config-
uration at 2000 cm−1, the di- and poly-hydride (SiH2)n mode at
2100 cm–1 and an intermediate bond-centred hydrogen, Si–H–Si,
identified as hydrides in a platelet-like configuration at 2060 cm−1 that
is not commonly observable in the case of nanocrystalline silicon, as
shown in Fig. 4(e) [38,39]. Fig. 4(f) shows the variation of the
microstructure factor (R), defined as the fraction of poly-hydride
component in the matrix,
R = I2100 / (I2000 + I2060 + I2100).
The fraction of Si–H–Si component, termed as surface passivation
index,
S = I2060 / (I2000 + I2060 + I2100)
has also been plotted in Fig. 4(f). It is significant to note that the sharp
decrease in the microstructure factor (R) that generally identifies fast
removal of structural imperfections from the network corresponds to
the rapid increase in the surface passivation index (S) of the matrix at
p > 1 Torr, corresponding to the transformation from highly crystalline
toward the amorphous dominated network prepared at a relatively high
growth rate.
In spectroscopic ellipsometry (SE) studies the measured dielectric
function, called ‘pseudo-dielectric function’, < ε > , usually involves
information about the entire thin film system: the substrate, the bulk of
the film, including the interfaces and surface over-layers. Fig. 5
presents the imaginary part of pseudo-dielectric function < ε2 >
obtained from the ellipsometry data, for the set of films. In general,
the oscillations of < ε2 > at low energies < 2.5 eV are related to the
composition of incubation layer and the film thickness, while at high
energies the magnitude of < ε2 > is largely controlled by bulk
composition and surface roughness [40].
For the film prepared at p=0.3 Torr, the pseudo-dielectric function
identifies two distinct shoulders at around 3.4 and 4.2 eV correspond-
ing to the critical points (CP) of the band structure of crystalline silicon,
E1 and E2, respectively. The prominent dual shoulders in the spectrum
demonstrate adequate crystallinity present in the film structure. In
general, higher magnitude of < ε2 > indicates higher density of the
network and the difference between intensities of these two shoulders
corresponds qualitatively to the degree of crystallinity of the network.
The < ε2 > spectra gradually reduced in magnitude accompanied by
two separate shoulders demonstrating the reduced crystallinity in the
S. Samanta, D. Das Journal of Physics and Chemistry of Solids 105 (2017) 90–98

Fig. 4. (a) Deconvoluted SiH wagging mode and SiHn rocking mode IR absorption components. (b) Variation in the bonded hydrogen content, CH, and the proportional strength of the
SiHn (n≥2) rocking mode absorption component, ΔI670, with increasing pressure. (c) The deconvoluted SiH2 bending and (SiH2)n wagging mode IR absorption components. (d)
Variations of the proportional strength of (SiH2)n poly-hydride wagging absorption component with pressure. (e) IR stretching mode absorption coefficient spectra deconvoluted into
components of Si-H mono-hydride and dihydride components and an intermediate bond-centred hydrogen, Si–H–Si, configuration with increasing pressure. (f) Effect of operating
pressure on the microstructure factor, R, and surface passivation index, S, of the nc-Si:H network.

films when prepared with increasing p. Furthermore, the difference in
the intensities of the two shoulders, [I(E1)–I(E2)], reduced significantly
at higher operating pressure in the plasma. Such lowering in the
intensity difference is closely related to the decreasing crystallinity and
continuously enhanced void in the bulk layer. It can also be related to
the reduced size of the Si nanocrystals, as when the diameter of the Si-
ncs reduces the oscillator strength changes between the lower and
higher energy states [40,41]. At a high pressure in the plasma,
p~1.5 Torr, the ε2-spectrum, with the absence of sharp critical points,
identifies the film network grossly deviating from its dominant crystal-
line structure. The results closely resemble the data obtained from
Raman and XRD-studies, both in crystalline volume fraction as well as
changing size of the nanocrystals issues.
The structural properties of the films have further been investigated
in detail by transmission electron microscopy. Various TEM features of
the films prepared at low, middle and high pressure, p=0.3, 0.6 and

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S. Samanta, D. Das Journal of Physics and Chemistry of Solids 105 (2017) 90–98

Fig. 5. Nature of variations of the imaginary part of pseudo-dielectric function < ε2 > at
different operating pressures. Inset represents the variation of [I(E1)–I(E2)] with
increasing pressure.
1.5 Torr, have been shown in Fig. 6(a)–(c), respectively. The plan-view
bright field TEM micrographs identify clusters of crystalline grains
which are randomly distributed within the amorphous matrix. The
volume density of the crystallites has been identified to reduce with
increase in pressure from 0.3 to 0.6 Torr and the matrix turned
towards an amorphous dominated one in samples prepared at
p=1.5 Torr, as observed from Fig. 6(a-i), (b-i) and (c-i), respectively.
The selected area diffraction patterns at the corresponding insets
identify < 111 > , < 220 > and < 311 > as the prominent crystal-
lographic planes in the nanocrystals. The corresponding high resolu-
tion images demonstrate lattice planes of silicon crystals with both <
111 > and < 220 > crystallographic orientations in Fig. 6(a-ii) and (b-
ii), while in Fig. 6(c-ii) hardly any such lattice plans are visible. Fig. 6(a-
iii), (b-iii) and (c-iii) represent the dark field scanning tunnelling
electron microscopy (DF-STEM) images of the samples prepared at
p=0.3, 0.6 and 1.5 Torr, respectively. In the images the darker contrast
identifies regions having lower atomic number or density which
generally includes amorphous silicon matrix and voids present in the
material. Bright areas are related to higher atomic number or density
which could be associated to Si-rich regions and mostly the clusters of
crystalline grains and a few isolated Si nanocrystallites [42].
The optical properties of the nc-Si:H films have been obtained from

<111> <220>
a-i a-ii a-iii

<111>
<311>
0.249 nm
0.3 Torr
0.3 Torr

b-i 0.189 nm b-iii

<220>
<111>

0.6 Torr
0.6 Torr b-ii

c-i c-ii c-iii

1.3 Torr 1.3 Torr

Fig. 6. TEM micrograph of nc-Si:H films prepared at (a) low p=0.3 Torr, (b) middle p=0.6 Torr and (c) high p=1.3 Torr. Insets show corresponding selected area diffraction patterns. (a-
ii), (b-ii) and (c-ii) High resolution images demonstrating extremely well defined c-Si planes of < 111 > and < 220 > orientations. (a-iii), (b-iii) and (c-iii) are the dark field TEM images
of corresponding films prepared at increased pressure.

95
S. Samanta, D. Das
Fig. 7. (a). The optical absorption spectra in Tauc's plots, (αhν)1/2 vs. hν, for nc-Si:H films prepared at different pressures. (b) Variation of optical gap, Eg and Tauc's constant, B, with
increasing pressure.
the wavelength dependent absorption coefficient calculated using both
the absorbance and reflectance spectra in the UV–vis region.
Considering the indirect-band gap nature of the material, Tauc's
equation, as
(αhν )1/2 = B(hν − Eg ),
has been employed to estimate the optical band gap of the films [43]. In
the above expression α, hν, and Eg are the absorption coefficient,
photon energy and Tauc's optical band gap, respectively, while the
proportionality constant B is termed as the Tauc constant. The (αhν)1/2
vs. hν plots for the film have been represented in the Fig. 7(a), which
identify a linear region over a reasonable span of photon energy axis for
each spectrum, confirming the relevance of the Tauc's law in the mixed-
phase materials. A gradual widening of the band gap from 1.77 to
1.785 eV happens to takes place on increase in p from 0.3 to 1.0 Torr.
However, for further increase in p beyond 1.0 Torr Eg increases
relatively faster and attains a magnitude of 1.82 eV at p=1.5 Torr
where a prominent structural transformation of the films from highly
crystalline to the amorphous prone network has been identified both
from XRD and Raman study.
The Tauc constant B in the Tauc's equation, in general, corresponds
to the disorder in the mixed-phase matrix in terms of deviation in the
bond angle and bond length of the silicon network which sharply
controls the band edges. The constant B as obtained from the slope of
the (αhν)1/2 vs. hν plots are plotted in Fig. 7(b) which show a gradual
Fig. 8. Variations of room-temperature dark conductivity (σD), photo conductivity (σPh)
and the photosensitivity of nc-Si:H samples prepared under different gas pressures in the
plasma.
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Journal of Physics and Chemistry of Solids 105 (2017) 90–98
increase in its magnitude at higher operating pressure. In general, the
constant B changes inversely with the width of the tail states, which is
larger for higher degree of disorder in the films. Accordingly, the film
grown at higher p > 1.0 Torr with enhanced magnitude of B consists of
lower defects and disorders as a consequence of increased amorphous
volume fraction in the matrix, as obtained from the structural studies
[44]. At increased p, the diminished crystalline volume fraction of the
nanocrystallites decreases the contribution of the surrounding grain
boundary defects.
Fig. 8 shows the variation of room temperature dark conductivity
(σD), photoconductivity (σph), and the photosensitivity (G) of the films
with the increase of gas pressure (p) in the plasma. The film prepared
at p=0.3 Torr exhibits a relatively high σD~8×10−4 S cm−1 consistent
with its highly nanocrystalline structure. With the increase in p, σD
monotonically reduces simultaneously exhibiting some photosensitiv-
ity. The Si:H films prepared at p=1.5 Torr, structurally at the virtual
termination of nanocrystallinity, demonstrates a low σD~10−9 S cm−1
with corresponding photosensitivity, G~600, by virtue of its nearly 50%
amorphous component in the network.
4. Discussion
In general, it has been identified that the growth of the films
gradually increases with the increase in the operating gas pressure in
the plasma; however, reaches at a virtual saturation with ~18 nm/min
at p≥1.3 Torr where the film network becomes amorphous-dominated
and consequently for which the usual growth rate should be further
accelerated. Accordingly, it is concluded that at p≥1.3 Torr the reactor
attained a SiH4 depleted plasma condition. At such high pressure the
electron temperature happens to be very low. Accordingly, the SiH4
dissociation energy is very small compared to both excitation and
ionization of H2 and He. So, the SiH4 dissociation appears significantly
high due to enhanced power coupling to the SiH4 and the growth rate
acquires saturation because of its limited supply in the reactor. In such
a state of affairs the nc-Si:H films of ~79% of crystallinity at a typical p
~0.6 Torr [Fig. 2(c)] obtained at ~13 nm/min appears to be reasonably
high compared to a similar crystalline material from only H2-diluted
plasma, reported in literature. The H2-dilution in the plasma maintains
a good crystallinity while the high deposition rate appears to be a
contribution from the He dilution and has been attributed to the
enhancement of the secondary electron emission coefficient induced by
He ions [22,23]. Formation of metastable helium (He*) and ionic
helium (He+) require comparatively low amounts of energy (20 eV and
24 eV, respectively). On de-excitation of metastable and ionic helium,
electronic energy is transferred to the reacting precursors and enhances
their mobility on the growing surface. Again, the atomic weight of
helium being much lower, ionic or metastable helium bombardment is
S. Samanta, D. Das
not as harmful as the bombardment of ionic precursors at the growing
surface. Moreover, helium bombardment increases the effective tem-
perature of the growing surface. All together accelerate the structural
relaxation and sustains a compact and ordered network [21].
From the XRD study it has been identified that the nc-Si:H films
prepared at p~0.6 Torr have the maximum I < 220 > /I < 111 > ~1.1, i.e.,
the dominant < 220 > crystallographic orientation. The Si-ncs have
the maximum size, d < 220 > ~15 nm, while the d < 111 > ~11 nm which
gradually reduces with p [Fig. 3(b)]. The average grain as estimated
separately from Raman study, d~12 nm, lies exactly in between d < 220
> and d < 111 > obtained from XRD, identifying an excellent agreement
in between. Notably, this dominant < 220 > crystallographic orienta-
tion could be associated to the maximum of the ultra-nanocrystalline
component fraction of crystallinity, (Xunc/Xnc), in the network obtained
in Raman study [Fig. 2(c)] [12,39]. It has been reported in literature
that the nanocrystallites with < 220 > crystallographic orientation
arises due to thermodynamically preferred grain growth, while the <
111 > orientation occurs from random growth [45]. The nc-Si films
with preferred < 220 > orientation are conducive to carrier transport
and are optimally suitable for use in the fabrication of stacked layer
devices e.g., solar cells [7]. Best values of open-circuit voltage (VOC) in
solar cells demonstrate low recombination losses in < 220 > textures
[46]. In this consideration, the nc-Si films prepared at p~0.6 Torr that
exhibit dominant < 220 > orientation, have been identified as the
optimum from the present set of samples.
Films prepared at p < 0.6 Torr are highly crystalline with mostly <
111 > crystallographic orientation and are associated with highly
defective poly-hydride networks at the grain-boundary regions
[Fig. 4(b) and (d)], which are further evident from its relatively high
microstructure factors (R) [Fig. 4(f)]. At p=0.6 Torr the optimum H-
content in the network corresponds to a relatively lower R and
increased S which identifies H attached to Si in a platelet like
configuration. The insertion of H into the stressed Si–Si bonds, during
the process of H induced crystallization of silicon thin film, leads to the
formation of bond-centred hydrogen, Si–H–Si forming platelet-like
hydrides within the nc–Si:H films [39,47–49]. At higher pressure the
H-insertion into the network takes place at a higher intensity of mono-
hydride mode accompanied by its platelet-like configuration. The H-
insertion reactions into the bond–centred location facilitate reorienta-
tion of the Si network which results in elimination of strained Si–Si
bonds and rigid atomic rearrangements [50]. However, it has been
identified that at such pressure, reduced di-hydride components of
silicon are assembled mostly in the form of clusters of di-hydrides,
(SiH2)n [Fig. 4(d)], and the minimization of internal strain thereof
induces preferred < 220 > orientation of growth in the network
[Fig. 3(c)]. At further high pressure similar changes in R and S are,
however, associated to rapid shift of the network structure towards an
amorphous dominated configuration.
With increase in deposition pressure from a low magnitude of
0.3 Torr, the width of sheath region is reduced, which results in
reduced energy of the ions bombarding on the growing surface. The
reduced ion bombardment is important in the development of device
quality film. However, with further increased deposition pressure
beyond a certain optimum, say 0.6 Torr in the present context, the
chemistry of the species reaching the substrate gets altered at reduced
mean free path of the species in the plasma region. At lower Pressure,
the radicals reaching the surface are mainly SiH3+/SiH3 and H. Thus,
the growth surface is well covered with SiH3 and H radicals. They
diffuse in the growing surface and result in the growth of nano-
crystallization. At increased pressure, the density of SiHx (x < 3)
radicals reaching the growth surface increases and thereby, limits the
growth of the nano-crystallites [13,24]. This is amplified in the form of
reduction of average crystallite size in the films and increase in
amorphous content, along with its subsequent increase in growth rate.
In contrary to the solely H2-diluted SiH4 plasma condition, (H2 + He)-
diluted SiH4, in the present case, produces dust-free plasma at
97
Journal of Physics and Chemistry of Solids 105 (2017) 90–98
moderately higher pressure that enables preparing Si:H films at a high
deposition rate at the onset of nanocrystallinity which is reported to be
highly useful in the fabrication of efficient solar cells.
He dilution to the SiH4 plasma in RF (13.56 MHz) PECVD has been
utilized effectively in the suppression of powder growth during high
rate deposition of mostly the a-Si thin films [51]. The a-Si:H films
having 7 at% H and an optical band gap of 1.73 eV were grown at
12 nm/min [52]. An increase in nc-Si component up to a volume
fraction of 32% at a deposition rate ~14.5 nm/min was reported by
Cheng et al. [53]. By critically optimizing the parametric conditions in
purely He-diluted SiH4 plasma a nanocrystalline network with a high
crystalline volume fraction (77%) and well-aligned crystallographic
lattice distribution attained in Si:H was reported by us for the first time
[54,55]. A high crystallinity of ~77.8% in the Si:H network at a growth
rate of ~12 nm/min was attained by Kim et al. [56] from an extremely
high He-diluted SiH4 plasma (3 sccm SiH4 in 500 sccm He) at a very
high gas pressure ~7 Torr where powder formation is likely to happen.
A wide optical gap of ~2.53 eV was demonstrated for such a material.
On the contrary, a narrowing of the optical gap to ~1.50 eV was also
been reported for the a-Si:H film prepared by He dilution to the SiH4
plasma [57]. The present article accounts nc-Si network of ~80%
crystallinity with average size of nanocrystals ~15 nm, by virtue of
introducing controlled addition of H2 to the He-diluted SiH4 plasma in
RF PECVD. A high fraction of the ultra-nanocrystalline component of
crystallinity, (Xunc/Xnc), in the film has been correlated to its dominant
< 220 > crystallographic orientation which are significantly important
in the performance of stacked layer devices like solar cells.
5. Conclusion
A detail study has been performed to elaborately investigate the
impact of variation of gas pressure in the SiH4 plasma diluted by an
equal amount of H2 and He with a gross dilution ratio of 99% on
various changes in the structural, optical and electrical properties of
the nanocrystalline silicon films prepared at 250 °C temperature in a
capacitively coupled RF-PECVD operated at 200 W RF (13.56 MHz)
power. In general, the nc-Si films prepared at a low pressure, p
~0.3 Torr are highly crystalline, ~80%, with grains of dominant <
111 > crystallographic orientation and of average size > 15 nm, < 5 at
% of bonded H which are mostly polyhydride in nature with high
microstructural factor R and a low surface passivation factor S, an
optical band gap of ~1.77 eV and a high σD~8×10−4 S cm−1. At an
optimum pressure, p~0.6 Torr, a dominant < 220 > crystallographic
orientation in the film has been correlated to the maximum ultra-
nanocrystalline component fraction of crystallinity, (Xunc/Xnc), in the
network which contains di-hydrides mostly in clusters and are grown at
~13 nm/min growth rate. The H2-dilution in the plasma maintains a
good crystallinity while the high deposition rate appears to be a
contribution from the He dilution and has been attributed to the
enhancement of the secondary electron emission coefficient induced by
He ions. At much higher pressure, p~1.5 Torr, the network approaches
towards the nanocrystalline to amorphous transition zone with ~51%
crystallinity, ~4 nm size of grains, a wide band gap, Eg~1.82 eV, and
demonstrates a low σD~10−9 S cm−1 with corresponding photosensi-
tivity, G~600 obtained at a high growth rate, d~18.3 nm/min, from
only 0.5 sccm flow of the feedstock SiH4. The Si:H films at the onset of
nanocrystallinity prepared at a high deposition rate in the SiH4
depleted plasma condition, appears promising in the fabrication of
efficient solar cells.
Acknowledgement
The work has been done under nano-silicon projects funded by
Department of Science and Technology (Nano-Mission Program) and
Council of Scientific and Industrial Research, Government of India.
S. Samanta, D. Das
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