Thin Solid Films 682 (2019) 1–9

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Thin Solid Films

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Influence of nitrogen partial pressure on optical properties of magnetron T

sputtered Al-Si-N thin films
⁎
Sonia,b, S.K. Mishraa, , S.K. Sharmab
a
CSIR-National Metallurgical Laboratory, Jamshedpur 831007, India
b
Indian Institute of Technology (ISM), Dhanbad 826004, Jharkhand, India

A R T I C LE I N FO A B S T R A C T

Keywords: Al-Si-N thin films were deposited on glass substrates at varying nitrogen partial pressure through magnetron
Nanocomposite hard coating sputtering. The effect of partial pressure of nitrogen gas in the gaseous mixture (argon and nitrogen) on the
Optical properties optical properties such as absorption coefficient, band gap energy, refractive index, extinction coefficient, di-
Nitrogen partial pressure electric constant of the film was investigated and correlation with structure was carried out. Nitrogen partial
pressure has a considerable effect on the film microstructure and consequently on their optical properties. The
transformation of the film from opaque to transparent is dependent on the partial pressure of nitrogen. The
crystallite size decreases from 27 to 19 nm with the rise in partial pressure of nitrogen from 3 × 10−1 Pa to
6 × 10−1 Pa but again increases as the pressure reaches 7.5 × 10−1 Pa. Refractive index of Al-Si-N coatings
shows normal dispersive behaviour. The transmittance, band gap energy, optical conductivity and dielectric
constant of the films were also studied as a function of nitrogen partial pressure.

1. Introduction
Al-Si-N is known to be a hard and transparent coating, suitable for
applications that require optical transparency and mechanical strength
simultaneously [1]. There are very few reports available on micro-
structural and mechanical aspects of magnetron sputtered nano-
composite Al-Si-N film [2–7]. These nanocomposite films can be used
for high temperature window application, transparent heat mirrors and
magneto optical discs [8–10]. A recent work on Al-Si-N coatings syn-
thesized by ion implantation and magnetron sputtering suggests that
they can be used as protective coating in spacecraft windows [11]. Si-
licon doped AlN is also potential coating for optoelectronic applications
[12,13]. For these applications along with their rigidity optical beha-
viour is very important to understand.
Optical properties like absorption coefficient, band gap energy,
optical conductivity, refractive index, extinction coefficient etc. provide
a lot of useful information regarding the optical response of the coating
which ultimately governs its suitability for applications. In order to
properly utilize the ternary Al-Si-N system for different optoelectronic
operations and protective optical coatings it is quite necessary to ex-
plore their optical behaviour in detail.
Optical activity of thin films relies on their structural and electronic
properties [14]. These properties depend on the growth condition of the
film and can be tailored by the deposition parameters. Magnetron
sputtering is one of the most suitable and efficient method to deposit
multicomponent nanocomposite Al-Si-N thin films, as it provides a
great flexibility and precise control over the deposition parameters.
Nitrogen partial pressure is one of the crucial parameter that affect the
nitride coating systems. Consequently, its influence on the optical
properties requires a detailed investigation. Very few reports are there
on optical properties with change in partial pressure of nitrogen for Al-
Si-N films. Lewin et al. have reported a comparative study between DC
magnetron sputtered and high power impulse magnetron sputtered
(HIPIMS) Al-S-N film with nitrogen variation [15]. This work was
mainly focussed on understanding the plasma characteristics along with
mechanical and structural properties evaluation. One more investiga-
tion based on the effect of nitrogen content on structural behaviour of
Al-Si-N coatings was carried out by Jiang and group [16]. The detailed
investigation of different optical properties of Al-Si-N thin films as the
function of nitrogen partial pressure is not reported yet. The present
studies try to fill the void that is required to have a better understanding
of structure dependent optical properties of Al-Si-N thin films which can
lead to the development of optoelectronic devices with enhanced per-
formance.
2. Experimental details
Al-Si-N thin films were deposited by sputtering an AleSi alloy target

⁎
Corresponding author.
E-mail address: suman@nmlindia.org (S.K. Mishra).

https://doi.org/10.1016/j.tsf.2019.05.006
Received 26 February 2018; Received in revised form 11 April 2019; Accepted 4 May 2019
Available online 07 May 2019
0040-6090/ © 2019 Elsevier B.V. All rights reserved.
Soni, et al. Thin Solid Films 682 (2019) 1–9

Table 1
Details of deposition conditions for Al-Si-N thin films.
Base pressure (Pa) Deposition pressure (Pa) Nitrogen partial pressure (Pa) Substrate temperature (°C) Power supply (DC) Film thickness, ± 10 (nm)

−4 −1
4 × 10 (1–2) 2 × 10 450 200 500
4 × 10−4 (1–2) 3 × 10−1 450 200 443
4 × 10−4 (1–2) 4.5 × 10−1 450 200 418
4 × 10−4 (1–2) 6 × 10−1 450 200 410
4 × 10−4 (1–2) 7.5 × 10−1 450 200 400

(86 wt% of Al and 14 wt% Si) in the reactive environment of nitrogen

gas through Magnetron Sputtering (HHV, Bangalore). The target in the
form of circular disc of 75 mm diameter and 3 mm thickness was cut
from the prepared ingot with the help of Electrical Discharge
Machining. The coatings were done on glass substrate as a transparent
base material is needed for optical characterization. The vacuum
chamber was evacuated up to 4 × 10−4 Pa. The partial pressure of
nitrogen was varied by adjusting the argon to nitrogen gas ratio with
the help of mass flow controllers. Different partial pressures were
maintained during deposition between (2.0 to 7.5)x10−1 Pa. The
chamber pressure and substrate temperature were maintained at (1–2)
Pa and 450 °C respectively during the entire deposition process. The
films were deposited at 200 W, DC Power supply for 120 min. The de-
tailed deposition parameters with film thickness obtained under dif-
ferent conditions are given in Table 1. The coating thickness was
measured by stylus profilometer (Taylor Hobson, Talysurf Series 2).
Structural properties were investigated through X-Ray Diffraction
(XRD, Bruker D8, Germany) using CuKα (λ = 1.5418 Å) radiation. The
crystallite size was calculated from the XRD pattern using Scherrer's
formula, Dav = kλ/βCosθ. Here, Dav = Average crystallite size,
λ = 1.5418 Å (Wavelength of X-Ray source, Cu kα), k = 0.94 for
spherical crystals and 0.89 for integral breadth of spherical crystals, it is Fig. 1. X-Ray Diffraction pattern of Al-Si-N thin films at different N2 partial
assumed 1 as 0.94 and 0.89 both round up to 1, β = Full width half pressure.
maximum (FWHM), in radian of the given peak and θ is the Bragg's
angle. The microstructure and Energy-dispersive X-Ray spectroscopy
no other peak present in the diffraction pattern which indicates that
(EDS) was studied by Field Emission Gun Scanning Electron Microscope
either silicon containing phase has remained in the solution or present
(FEGSEM, Philips, Netherland). Voltage was set at 7 kV for capturing
as amorphous Si3N4.
the images, the elemental composition was obtained by EDS (EDAX,
The crystallite size of the films was calculated using the Scherrer's
USA) at 10 kV with zero tilt and was ZAF corrected automatically by an
relation [17] using (100) peak, shown in Fig. 2. The crystallite size was
inbuilt software. The detector type was SDD Apollo 40. The optical
found to decrease from 27 nm to 19 nm as the nitrogen partial pressure
characterization was performed using UV–Visible Spectrometer (Shi-
increased from 3 × 10−1 Pa to 6 × 10−1 Pa but again it increased to
madzu, UV 2550, Japan) in the UV–Visible range. The refractive index
and extinction coefficient was calculated by envelope method proposed
by Swanepoel and Jakopic whose detailed calculation is given in their
respective section.

3. Results and discussion

3.1. Structural Investigation

3.1.1. X-Ray diffraction and crystallite size calculation

Fig. 1 represents the XRD of Al-Si-N thin films deposited at different
partial pressure of nitrogen. The formation of hexagonal wurtzite AlN
phase starts when the partial pressure of nitrogen was 3 × 10−1 Pa.
Below this particular value of N2 partial pressure i.e. at 2 × 10−1 Pa,
only Al peaks were found (JCPDS Card no. 89-3657), which means, a
higher nitrogen partial pressure is required for the formation of AlN.
The peaks in the diffraction pattern matching with the hexagonal AlN
structure (JCPDS Card no.25-1133) was observed for all the films de-
posited at a nitrogen partial pressure lying in the range (3–7.5) x10−1
Pa. A preferential growth in (100) direction was also observed though
the films were polycrystalline as (110) peak was also present. However,
as the nitrogen partial pressure was increased from 3 × 10−1 Pa to
4.5 × 10−1 Pa and subsequently to 6 × 10−1 Pa, intensity of both the
peaks diminishes but with a further increase in the partial pressure to Fig. 2. Magnified plot of (100) peak for Al-Si-N films deposited at different N2
7.5 × 10−1 Pa, the (100) peak again becomes more intense. There was partial pressure.

2
Soni, et al. Thin Solid Films 682 (2019) 1–9

Table 2 Table 4
Crystallite size calculation using Scherrer's formula. Average roughness values for Al-Si-N films on glass substrate deposited at dif-
ferent N2 partial pressure.
Nitrogen partial pressure 2θ position FWHM (β, Crystallite size
(Pa) (Degree) Degree) (Dav, nm) Nitrogen partial pressure (Pa) Average roughness, Ra (μm)
−1
3 × 10 33.254 0.34006 27 2 × 10−1 0.06
4.5 × 10−1 33.254 0.39238 23 3 × 10−1 0.02
6 × 10−1 33.254 0.47799 19 4.5 × 10−1 0.03
7.5 × 10−1 33.254 0.39319 23 6 × 10−1 0.02
7.5 × 10−1 0.05

23 nm as the N2 partial pressure increased to 7.5 × 10−1 Pa (Table 2).
The enlarged view of the (110) peak showed a remarkable shift in the
peak position for the film deposited at 7.5 × 10−1 Pa N2 partial pres-
sure, which indicates lattice distortion (Fig. 2). A dotted line is drawn in
the middle of the peak position that corresponds to 3 × 10−1 Pa N2
partial pressure in order to show the characteristic peak shift. It can be
seen that there is no shift in peak position when the N2 partial pressure
is increased from 3 × 10−1 Pa to 4.5 × 10−1 Pa but as the pressure
reaches 6 × 10−1 and 7.5 × 10−1 Pa the peak shifts towards right from
the dotted line i.e. towards the higher angle (2θ value). This shift can be
attributed to the increase in the value of lattice parameter ‘c’. A suffi-
ciently higher value (7.5 × 10−1 Pa) of nitrogen partial pressure leads
to a large number of N atoms incorporated in the AlN lattice which can
result in the expansion of the lattice parameter ‘c’.
For quantitative analysis of the peak shifting phenomena due to
strain produced in the crystal as a result of increasing nitrogen partial
pressure, the values of lattice parameters were calculated using the
basic formula for hexagonal closed pack system [18] as given below,
1 4 h2 + hk + k 2 ⎫ l2
= ⎧ + 2
d2 3⎨
⎩ a2 ⎬
⎭ c
here'd’ is the interplanar spacing, (hkl) are the miller indices and ‘a’ and
‘c’ are the lattice parameters. The obtained values of ‘a’ and ‘c’ are given
in Table 3. The value of ‘a’ was calculated using the ‘d’ value and miller
indices of the (100) peak of the XRD pattern. In order to calculate ‘c’,
the ‘d’ value of (101) peak from the same JCPDS card which matched
the peaks of the obtained XRD pattern was used. It can be seen that
there is no change in the value of ‘c’ when the N2 partial pressure in-
creases from 3 × 10−1 Pa to 4.5 × 10−1 Pa, that's why there is no shift
in peak position for this transition in partial pressure. However, as the
N2 partial pressure is further increased to 6 × 10−1 and 7.5 × 10−1 Pa,
the ‘c’ value increases signifying the strain produced in the lattice due to
incorporation of nitrogen which is responsible for the shift in peak
position.
3.1.2. FEGSEM analysis
The average surface roughness values of Al-Si-N thin films deposited
at different N2 partial pressure is given in Table 4. Fig. 3 shows the
microstructure of Al-Si-N films deposited at different N2 partial pres-
sure. The grains become finer as the N2 partial pressure increased from
2 × 10−1 Pa to 3 × 10−1 Pa and the surface becomes smoother. This
fact is also supported by the obtained average roughness values. In-
itially the microstructure was cauliflower type but later fine grain
structure growth was observed with further increase in partial pressure
Table 3
Value of Lattice parameters at different N2 partial pressure for Al-Si-N thin films
having hcp structure.
Nitrogen partial pressure (Pa) Lattice parameters (Å)
a=b c given in Table 3. The absorption edge of the films deposited at N2
3 × 10−1 3.1074 5.0188
4.5 × 10−1 3.1085 5.0062
6 × 10−1 3.0972 5.0702
7.5 × 10−1 3.0981 5.0701
Note: The above measurements were carried out on four samples for each N2
flow rate at different places and the results were averaged.
of nitrogen to 4.5 × 10−1 Pa. The surface morphology transformed into
a denser one when the N2 partial pressure is again increased to 6 and
7.5 × 10−1 Pa. This also agrees to the findings of Domokos et al. [19]
and Surasing et al. [20] where they too found grain refinement with
increase in nitrogen partial pressure. Similar kind of morphology with
varying nitrogen content was observed by Jiang et al. [16]. The EDS
analysis of Al-Si-N films is shown in Table 5. The substrate composition
was removed and the result shows the atomic percentage of the ele-
ments comprising the coating. The coating composition when expressed
in terms of (Al + Si)/N ratio, shows that this particular ratio decreases
to about half as the N2 partial pressure increases from 2.0 × 10−1 Pa to
3.0 × 10−1 Pa and remains almost same with further increase in the N2
partial pressure and decreases again when N2 partial pressure reaches
6.0 × 10−1 Pa and with subsequent increase in N2 partial pressure a
rise in the ratio is observed. Though a particular trend is not followed
by the (Al + Si)/N ratio, it ca be summarized that AleSi rich phases are
there with low nitrogen content for the lower nitrogen partial pressure,
at 6,0 × 10−1 Pa, properly nitrided AleSi phases are formed.
3.2. Optical characterization
3.2.1. Transparency and transmittance
Nitrogen content has a substantial influence on film transparency.
The film deposited at 2 × 10−1 Pa N2 partial pressure was opaque. The
reason for opacity is low nitrogen partial pressure which may be in-
sufficient for the formation of AlN phase. The absence of AlN phase is
revealed in the XRD pattern of Al-Si-N film (Fig. 1) deposited at N2
partial pressure, 2 × 10−1 Pa. Only Al metal phase peaks were found
resulting into an opaque coating. The onset of transparency in the Al-Si-
N film initiates with the formation of AlN wurtzite phase, which oc-
curred with increase in nitrogen partial pressure to 3 × 10−1 Pa, as was
discussed above in XRD Section 3.1.1.
The optical properties of nanocomposite Al-Si-N thin films were
investigated by the transmittance spectra as a function of wavelength.
The dependence of transmittance on the nitrogen content of Al-Si-N
films is shown in Fig. 4. The interference pattern present in the spectra
is due to reflection of light between the air-film and film-substrate in-
terface. The film corresponding to N2 partial pressure, 3 × 10−1 Pa
have transmittance value of about 90%. For the films deposited at
4.5 × 10−1 and 6 × 10−1 Pa nitrogen partial pressure there is a slight
increase in the value of transmittance in wavelength range (500–800)
nm but at shorter wavelength, the coatings start absorbing light. When
nitrogen gas content is again increased by increasing its partial pressure
to 7.5 × 10−1 Pa, a little drop in transmittance value was recorded.
This trend of transmittance could be due to the fact that the formation
of AlN and Si3N4 become more profound with rise in N2 partial pressure
[21], which is confirmed through the EDS carried out for Al-Si-N films,
partial pressure 3 × 10−1 and 4.5 × 10−1 Pa lies at a wavelength of
461 nm but as the partial pressure reached 6 × 10−1 Pa there is a blue
shift in the absorption edge i.e. it shifts towards a lower value of wa-
velength, 416 nm. The shifting in absorption edge is the consequence of
crystallite size variation with change in the N2 partial pressure. As the

3
Soni, et al. Thin Solid Films 682 (2019) 1–9

Fig. 3. FEGSEM images of Al-Si-N thin films deposited on glass substrate at varying N2 partial pressure.

Table 5 shorter wavelength i.e. blue shift. Moreover, a red shift in absorption
Elemental composition of Al-Si-N thin films (on stainless steel substrate) at edge is observed in the case of the film deposited at N2 partial pressure,
different N2 partial pressure by EDS. 7.5 × 10−1 Pa i.e. the edge shifts towards the longer wavelength,
Nitrogen partial pressure (Pa) Element atomic % 451 nm which is again due to increase in the crystallite size, similar
observations were also reported by Shinho Cho et al. [22].
Al Si N

2 × 10−1 69.4 10.6 19.9 3.2.2. Refractive index (n) and extinction coefficient (k)
3 × 10−1 61.9 5.7 32.3 The refractive index (n) is calculated by envelope method proposed
4.5 × 10−1 61.4 8.9 29.6 by Swanepoel [23]. This method is applicable to thin films having
6 × 10−1 58.1 7.1 34.8 thickness much lower than the substrate thickness. Here in case of Al-Si-
7.5 × 10−1 59.3 9.8 30.8
N film the thickness lies in the range (400–500) nm and the glass
Note: The above measurements were carried out on four samples for each N2 substrate is about 1.2 mm thick. Also, the interference pattern present
flow rate. in the transmittance spectra also assist in calculating ‘n’ through this
method. So, this method is quite suitable for calculation of optical
constants of Al-Si-N coatings.
Using the software, Origin Pro, two curves designated as Tmax and
Tmin are drawn by parabolic interpolation of the peaks and valleys that
is corresponding maxima and minima of the interference fringes in the
transmission spectra as obtained by UV–Visible spectroscopy which are
known as envelope curve. Fig. 5 shows a typical envelope curve for the
transmission spectra corresponding to 7.5 × 10−1 Pa N2 partial pres-
sure. According to Swanepoel, ‘n’ is given by,

n= [N + N 2 − ns2 ⎤
⎥
⎦
The value of N in weak and medium absorption region is calculated
from the equation below,

Tmax − Tmin n2 + 1
N = 2ns × + s
Tmax Tmin 2

here ns is the refractive index of substrate which is evaluated from the

formula,
Fig. 4. Transmittance spectra of Al-Si-N thin films deposited at different N2
partial pressure. 1 ⎛ 1 − 1⎟⎞
ns = + ⎜
2
Tmax ⎝ Tmax ⎠
nitrogen partial pressure is increased from 4.5 × 10−1 Pa to 6 × 10−1 Generally, the value of Tmax is the maximum transmittance in the
Pa the crystallite size reduces from about 23 nm to 19 nm. This reduc- transparent region.
tion in crystallite size can bring a quantization effect in the density of The calculated ‘n’ value was plotted as a function of wavelength
states which ultimately leads to the shifting of absorption edge towards (Fig. 6a). The figure shows that ‘n’ exhibits normal dispersive behaviour

4
Soni, et al.
Fig. 5. Envelope curve of Al-Si-N film at 7.5 × 10−1 Pa N2 partial pressure for
refractive index calculation.
as there is a decrease in refractive index with increasing wavelength for
all the films deposited at different nitrogen partial pressure. The value
of ‘n’ at 633 nm wavelength slightly increases in the range (1.54–1.58)
with increase in nitrogen partial pressure from (2 × 10−1-7.5 × 10−1)
Pa which means that the film grows denser with the increase in N2
partial pressure. The reported value of ‘n’ for Al-Si-N thin film lies in the
Fig. 6. Refractive index and Extinction coefficient Vs Wavelength plots obtained by envelope method (a and b) and inversion of s-transmission data (c and d).
5
Thin Solid Films 682 (2019) 1–9
range 1.9 to 2.1 [15].
Extinction coefficient (k) is the measure of light absorbance in a
given medium. For transparent films its value is ideally zero. Al-Si-N
films are not perfectly transparent as glass so it will have lower but a
non-zero ‘k’ value. Extinction coefficient is given by, k = αλ/4π [24].
Here, α is extinction coefficient and λ is the wavelength. The variation
of ‘k’ with wavelength is shown in Fig. 6b. At shorter wavelength range
(300–450) nm, there is a rapid decrease in the ‘k’ value. The value of ‘k’
is highest for the film deposited at 7.5 × 10−1 Pa as it possesses the
lowest transmittance. The films deposited at rest of the N2 partial
pressure have almost a similar value of ‘k’ and it becomes almost con-
stant in longer wavelength range (500–800) nm and its value drops as
most of the light is transmitted in this region.
As the envelope method gives an estimation of ‘n’ and ‘k’, the values
of optical constants were also derived using the process given by
Jakopic [25] for verification. It can be suitably applied on weakly ab-
sorbing thin films on a transparent substrate. This method utilises the
inversion of the s-polarized transmittance of the thin film by estab-
lishing relation between the transmittance of the free standing film,
substrate and the thin film on substrate. The real (n) and imaginary (k)
parts of the complex refractive index were calculated indirectly from
the real and imaginary parts, ηF and γF of the normal component of
wave vector q of the incident light entering the thin film medium.
Analytical equations were formulated with the help of the envelope
curves Tmax and Tmin for calculation of ηF and γF as given below.
ηF + η0 η + η1 Tmax − Tmin
X= × F ×
ηF − η0 ηF − η1 Tmax + Tmin
Soni, et al.
here, η0 = 1(Refractive index of air) and η1 is the refractive index of the
substrate.
ηF = B+ B2 − η02 η12
η02 + η12 Tmax − Tmin
= + 2η0 η1 ×
2 TmaxTmin
lnX ⎞
B γF = −⎛
⎝ 4πνt ⎠
here, ν is the wavenumber and t is the film thickness.
The obtained values of ‘n’ and ‘k’ were plotted with wavelength
(Fig. 6c and d respectively). The values for ‘n’ lies in the range
(1.64–1.7) at 633 nm wavelength for films deposited at nitrogen partial
pressure between 3 × 10−1 Pa to 7.5 × 10−1 Pa. There is a slight in-
crease in the values of ‘n’ extracted from the inversion of s-transmit-
tance data. The obtained ‘k’ values are also one order higher than those
computed by envelope method. Moreover, the variation of ‘k’ with
wavelength shows an oscillatory behaviour (Fig. 6d) which is due to the
multiple beam interference in the thin film. In Fig. 6b no such beha-
viour is obtained as the absorption coefficient used for calculation of ‘k’
was extracted from the transmittance spectra which is free from the
interference pattern through envelope method.
3.2.3. Absorption and band gap energy study
Absorption coefficient (α) is yet another crucial parameter that
governs the overall optical behaviour of Al-Si-N thin films. Generally, it
1 1
is calculated from the following formula [26], α = t ln T , where ‘α’ is
the absorption coefficient, ‘t' is film thickness and ‘T' is the transmit-
tance. But this formula is valid for a bulk system where the light travels
only through air to the specimen. But in case of thin films multiple
reflection takes place as the light is travelling through three interfaces
namely air-film, film-substrate and substrate-air resulting into inter-
ference pattern in the transmittance spectra. Thus in order to apply the
above formula the experimentally obtained transmission spectra is
transformed into interference free spectra using the formula,
Tα = Tmax Tmin , obtained from envelope method proposed by Swanepol.
So now in the formula for calculation of ‘α’, T can be replaced by Tα.
Fig. 7 shows the dependence of ‘α’ on photon energy for films de-
posited at different N2 partial pressure. The spectra show that at lower
photon energies ‘α’ was slightly affected by the nitrogen partial pres-
sure. The highest value of ‘α’ at the absorption edge, 4 × 103 cm−1, was
recorded for the Al-Si-N film deposited at 7.5 × 10−1 Pa nitrogen
Fig. 7. Variation of absorption coefficient, α with photon energy at different N2
partial pressure.
6
Thin Solid Films 682 (2019) 1–9
partial pressure. For higher photon energies (> 3.5 eV) there is a sharp
increase in ‘α’ with increasing N2 partial pressure.
Band gap energy of Al-Si-N films is calculated from Tauc relation
[27],
(αhν) = A(hν–Eg) n
here, hν is the photon energy, A is proportionality constant, Eg is the
band gap energy and ‘n’ depends on whether the transition between
valence and conduction band is direct or indirect. ‘n’ assumes values ½
and 2 for direct and indirect transitions respectively. As the deposited
Al-Si-N films are expected to possess nanocomposite structure com-
prising of both crystalline and amorphous phase, transitions of both
kinds i.e. direct and indirect are possible. The band gap was evaluated
by extrapolating the linear region of (αhν)2 Vs hν and (αhν)1/2 Vs hν
curve to (αhν)2 = 0 for direct and indirect transitions respectively. Fig.
(8a-8d) depicts the direct band gap energy plots at varying nitrogen
partial pressure.
The band gap increases from 2.57 eV to 3.38 eV with increasing N2
partial pressure from 3 × 10−1 Pa to 7.5 × 10−1 Pa. One of the factor
that could be responsible for the widening of band gap is the increasing
strength of the bond i.e. formed between metallic Al and Si with ni-
trogen with increase in N2 partial pressure, as a result of which higher
energy is required for the transition of electrons [28]. One more reason
for higher values of band gap with N2 partial pressure can be attributed
to the crystallite size. The barrier height decreases with increasing
crystallite size, thus band gap is inversely proportional to the grain size.
The relation between crystallite size and barrier height was established
by Slater in 1956 [29]. From crystallite size calculations by XRD result
it was previously shown that it decreases with increasing N2 partial
pressure up to 6 × 10−1 Pa but slightly rises with further increase in N2
partial pressure. The band gap energy of Al-Si-N thin films also follow
the same trend for corresponding partial pressure of nitrogen as shown
by the crystallite size except the film deposited at 7.5 × 10−1 Pa ni-
trogen partial pressure. The indirect band gap also increases as the
partial pressure of nitrogen was increased from 3 × 10−1 Pa to
7.5 × 10−1 Pa and lies in the range (1.35–2.22) eV.
In order to evaluate the exponent ‘n’ for understanding the nature of
transition taking place in Al-Si-N thin films, the Tauc equation is re-
arranged as,
ln(αhυ) = lnA + n ln (hυ − Eg )
An estimation of band gap energy, Eg was obtained by fitting the
linear portion of absorption coefficient Vs wavelength plot (Fig. 8e), the
film deposited at 3 × 10−1 Pa N2 pressure was used) The linear portion
is extrapolated to α = 0 and the value of Eg corresponding to that
particular value of wavelength which was crossing through the extra-
polated linear fit was put in the above equation. The plot between ln
(hυ-Eg) and ln(αhν) will give the value of ‘n’ which is the slope of the
above equation. It can be seen in Fig. 8e that there are two linear
portions which are extrapolated to α = 0 indicating two kinds of
transition in the Al-Si-N film deposited at 3 × 10−1 Pa. Similarly, all
the films deposited at varying N2 partial pressure have two types of
transition, thus giving two different values of band gap energy. Con-
sequently, the exponent ‘n’ is also having two values. The ‘n’ values
obtained for films deposited at varying N2 partial pressure along with
their band gap energy is given in Table 6. It shows that the exponent ‘n’
is deviating from ½ and 2 as suggested for direct and indirect transition.
It may be due to the disorderness in the film microstructure due to
presence of irregularities at the interface between two crystallites as the
result of matrix phase which gives rise to change in the arrangements of
density of states for the conduction and valence band [30]. A plot be-
tween ln(hυ-Eg) and ln(αhν) is shown in Fig. 8(f) for the film deposited
at 3 × 10−1 Pa nitrogen partial pressure which depicts the value of
exponent ‘n’.
Soni, et al. Thin Solid Films 682 (2019) 1–9

Fig. 8. Band gap plots at varying N2 partial pressures (a to d), absorption coefficient Vs Wavelength and ln(hν) plot for calculation of n for the film deposited at
3 × 10−1 Pa N2 partial pressure (e and f).

Table 6 Fig. 9a that, at absorption edge the value of ɛr lies in the range (4–9) for
Value of exponent ‘n’ calculated from Tauc relation for Al-Si-N films deposited the film deposited at 7.5 × 10−1 Pa N2 partial pressure. The Al-Si-N
at different N2 partial pressure. films whose nitrogen partial pressure lies in the range (3–6) x10−1 Pa
Nitrogen partial pressure Value of exponent ‘n’ Band gap energy(eV) have ɛr between 2.5 and 3.5 at the absorption edge and decreases ex-
(Pa) ponentially at lower photon energy as the films start absorbing the light
n1 n2 Eg1(n1) Eg2(n2) at lower energies. The nature of curve for ɛi (Fig. 9b) also follows the
same trend as ɛr. The value of ɛr for an another transparent coating NiO
3 × 10−1 0.6280 0.9060 2.26 1.75
4.5 × 10−1 0.9198 1.1564 2.50 2.13 which is having a vital application in the field of optoelectronics is in
6 × 10−1 0.7290 1.099 3.01 2.46 the range of approximately 2–9 [32] but being an oxide based coating it
7.5 × 10−1 0.7892 1.820 3.12 1.86 suffers from environmental instability due to which it is not suitable for
applications that involve metals which are prone to oxidation, whereas
Al-Si-N film does not have such an issue. The variation of ɛr and ɛi with
3.2.4. Dielectric constant photon energy follows the same trend as that of ‘n’ and ‘k’. The simi-
Dielectric constant gives an idea of polarization in a material. This larity can be accounted from there relation with Maxwell eqs.
effect comes into picture when electromagnetic radiation in the form of
light interacts with the Al-Si-N coating. Visible light of different fre-
quencies give rise to a dipole moment due to electron cloud displace- 3.2.5. Optical conductivity
ment at a given frequency. The real and imaginary dielectric constants The response of a material in terms of transition of electrons from
are given by [31], valence to conduction band when illuminated by photons of specific
energy is known as optical conductivity. It can be determined by the
ɛr = n 2–k2, ɛimg = 2nk equation [33],
σopt = αnc/4π
here, ɛr and ɛi are real and imaginary dielectric constant and n and k
are refractive index and extinction coefficient of the film respectively here, σopt is the optical conductivity, α is the absorption coefficient,
defined earlier. Fig. 9a and b shows the variation of real and imaginary ‘n’ is the refractive index and ‘c’ is the velocity of light. The variation of
parts of dielectric constant with photon energy. It is observed from σopt with photon energy at different N2 partial pressure is plotted in

7
Soni, et al.
Fig. 9. Variation of ɛreal and ɛimaginary with photon energy for Al-Si-N films at different N2 partial pressure.
Fig. 10. Variation of optical conductivity with photon energy of Al-Si-N coat-
ings at different N2 partial pressure.
Fig. 10. The graph shows a gradual increase in σopt with photon energy
up to a value that corresponds to its absorption edge as σopt is the
function of ‘α’ and then, there is an exponential rise in σopt after ab-
sorbing the photon of a particular energy that leads to the excitation of
electrons from valence to conduction band.
It can be interpreted from Fig. 10 that σopt has almost similar values
for the Al-Si-N films deposited at different N2 partial pressure for lower
photon energies. But for higher photon energies a sharp rise is observed
as the N2 partial pressure increases from 2 × 10−1 Pa to 7.5 × 10−1 Pa.
This trend is similar to ‘α’ as σopt is dependent on it.
4. Conclusions
The optical behaviour of Al-Si-N thin films depend markedly on the
nitrogen partial pressure during deposition. The films transformed from
opaque to transparent at the 3 × 10−1 Pa partial pressure of nitrogen.
The presence of metallic aluminium in the film deposited a lower N2
partial pressure (2 × 10−1 Pa) makes the coating opaque.
Transmittance increases with increasing N2 partial pressure (2–6)x10−1
Pa but again decreases with increase in partial pressure to 7.5 × 10−1
Pa. Both direct and indirect band gap energy increases with increase in
nitrogen partial pressure in the range (2.57–3.38) eV and (1.35–2.23)
8
Thin Solid Films 682 (2019) 1–9
eV respectively. The value of exponent ‘n’ of Tauc equation deviates
from the standard values assigned for the allowed transitions. The mi-
crostructural investigation suggests that the grains become finer with
the addition of N2 content as the partial pressure of nitrogen gas in-
creases gradually. The ‘n’ value undergoes a slight increase in the range
(1.54–1.59) with increase in N2 partial pressure from 2 × 10−1 Pa to
7.5 × 10−1 Pa as calculated using envelope method. It's value increases
slightly and lies in the range (1.64–1.70) through inversion of s-trans-
mittance spectra. The ‘k’ value was also one order higher by this
method than that computed through envelope method. The variation of
σopt and ‘α’ with photon energy followed the similar behaviour, there
values at shorter wavelength are almost unaffected by the nitrogen
partial pressure and at longer wavelengths a sharp increase is observed.
The value of σopt at absorption edge is highest for the film at
7.5 × 10−1 Pa N2 partial pressure which is about 2 × 1013 s−1. For the
films at lower partial pressure of nitrogen this value is about 1.5 × 1013
s−1. ɛr and ɛi show the similar trend as shown by the variation of ‘n’ and
‘k’ with photon energy.
Acknowledgement
One of the author, Soni, is thankful to CSIR, New Delhi for providing
Senior Research Fellowship to carry out this work.
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