Sensors and Actuators A 276 (2018) 328–334

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Sensors and Actuators A: Physical

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

X-ray sensing performance of ZnS:Cr film synthesised by a chemical

bath deposition technique
M.P. Sarma a , J.M. Kalita a,b,∗ , G. Wary a
a
Department of Physics, Cotton University, Guwahati, 781001, India
b
Department of Physics and Electronics, Rhodes University, P O Box 94, Grahamstown, 6140, South Africa

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

Article history: We report the X-ray sensing performance of Cr doped ZnS film synthesised by a chemical bath deposition
Received 21 December 2017 technique and present a comparative study of the detection sensitivity between the Cr doped and an un-
Received in revised form 22 April 2018 doped ZnS film. Due to doping of Cr in ZnS, the X-ray diffraction peaks of ZnS shifted towards higher
Accepted 27 April 2018
diffraction angle, average crystallite size decreased and microstrain as well as the roughness of the films,
Available online 30 April 2018
increased. In addition, the band gap also decreased from 3.38 to 3.23 eV. Current-voltage characteristics
of the films were studied under dark condition and under X-ray radiation. The doping of trivalent Cr in
Keywords:
ZnS matrix offered excess electrons for conduction. As a result, the conductivity of the doped film was
ZnS
Thin film
found to be ∼10 times greater than that of the un-doped film. The doped films under X-ray give more
Doping current than the un-doped one. This makes the doped films more useful than the un-doped one. However,
X-ray the un-doped film was found to be more effective to detect any change in energy of the X-ray radiation.
Sensor Regarding response-time, the rise time of radiation induced current in the doped film is found to be 0.80 s
which is shorter than that in the un-doped film. On the other hand, the decay time in the doped film is
1.67 s which is longer than that in the un-doped film. The magnitudes of the time differences between
the doped and un-doped films were not very large and therefore, the effect of doping on the response
time is negligibly small. Owing to higher conductivity, the Cr doped films are found to be more useful
than the un-doped one.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction
Zinc sulphide (ZnS) is a wide band gap semiconducting material
belonging to group II–VI. Due to its unique physical properties, it
has been the subject of numerous studies. It is a very useful material
for the fabrication of various photonic and optoelectronic devices
like solar cells and many electroluminescent devices. It has also
become a promising option for the synthesis of gas sensor [1], ultra-
violet (UV) radiation sensor [2–4] as well as pH sensor [5]. Most
recently, it was reported that ZnS thin film could be used as an X-
ray radiation sensor under some specific conditions [6]. The report
showed that when a voltage between 0.5 and 6.0 V was applied
across a ZnS film, the current under X-ray irradiation was ∼10 times
higher than the dark current. It was shown that the enhancement
of current under X-ray irradiation could be used as a way to detect
X-ray radiation. Although the film can be used to detect X-ray, the
∗ Corresponding author at: Department of Physics, Cotton University, Guwahati,
781001, India.
E-mail address: jitukalita09@gmail.com (J.M. Kalita).
amount of current is not very high in both dark and X-ray irra-
diation conditions. For example, when a bias-voltage of 1.0 V was
applied across the film, the current under X-ray radiation was only
∼4 × 10−10 A. To take account such small currents, high-precision
electrometer is required, which hamper the development of low-
cost X-ray sensor. Therefore, it is important to increase the amount
of current up to a certain level so that it can be measured by a com-
mon electrometer. In order to increase the current, although, one
can use higher bias-voltage, the detection sensitivity of the film
was reported to decrease with increase in bias-voltage [6]. There-
fore, doping of ZnS by some trivalent impurity can be expected to
meet the requirement.
Doping of ZnS by different elements has been found to alter its
various properties. Theoretically, it has been established that ZnS
doped with transition-metals, like Cr, Fe and Ni can become half
metallic, ferromagnetic and 100% spin polarise [7]. The impurity
states of the dopants play a vital role in improving the transi-
tion probabilities and electronic energy structures of the host ZnS
matrix [8]. Among all the transition-metal dopants, the Cr doped
ZnS (ZnS:Cr) has been considered as a model object for spec-
troscopy. The ZnS:Cr thin film synthesised by molecular beam and

https://doi.org/10.1016/j.sna.2018.04.044
0924-4247/© 2018 Elsevier B.V. All rights reserved.
 M.P. Sarma et al. / Sensors and Actuators A 276 (2018) 328–334 329

pulsed laser deposition technique has been found to be a useful

material for intermediate band solar cell [9]. The doping of ZnS by
Cr was found to reduce the band gap of the host and increased the
dielectric constant [10]. Due to smaller band gap and greater value
of dielectric constant of ZnS:Cr than that of ZnS, it was speculated
that the electrical conductivity of ZnS can be increased by doping
of Cr [10].
As stated earlier, to develop a low-cost X-ray sensor using ZnS
thin film, it is essential to increase the electrical conductivity of
the film. Literature shows that doping of ZnS by Cr could be a good
option to achieve that criterion. The aim of this work is to synthe-
sis Cr doped ZnS films under various concentrations of the dopant
using a chemical bath deposition (CBD) method and to study any
change of structural and optical properties occur after doping of Cr.
Finally, to report the possible improvements of the X-ray radiation
sensing properties of ZnS:Cr over the ZnS film.

Fig. 1. XRD patterns of ZnS, ZnS:Cr-I and ZnS:Cr-II films. The insets show the shifting
2. Experimental details
of (111), (200), (220) and (311) peaks after doping.

2.1. Sample preparation

The films were synthesised on glass substrates by a CBD method.
CBD is a simple and cost-effective method of deposition of thin film.
It is a controlled process of precipitation of chemical compounds on
a solid substrate from a solution of chemical precursors. Using this
method, stable, adherent, uniform and hard films can be deposited.
The principal chemicals used to deposit the films were thiourea
[SC(NH2 )2 ] (purity 99.99%) as a sulphide ion source, zinc acetate
[Zn(CH3 COO)2 ] (purity 99.99%) as zinc ion source and CrO3 (purity
99.99%) as chromium ion source. In a recent study, it was noted
that the ZnS film synthesised at 0.20 M has better lattice quality
and suitable for X-ray sensor [6]. Therefore, in the present study,
we choose to dope Cr on 0.20 M ZnS film only. At first, 0.05 M and
0.10 M solutions of CrO3 were prepared individually. Now 30 ml
0.20 M solution of zinc acetate was mixed with the 30 ml equimo-
lar solution of thiourea in a glass beaker and the mixture solutions
were stirred. In the mixture solution, 0.05 M solutions of CrO3 was
poured and the whole solution was kept stirring for 40 min. To
improve the homogeneity and the growth rate, 15 ml of 1.00 M
hydrazine hydrate [(NH2 )2 ] solution was also mixed during stirring
condition. The pH of the solution was maintained between 9 to 10
by adding ammonia solution. The reaction bath temperature was
fixed at 343 K. After stirring, chemically cleaned glass substrates
were vertically immersed in the solution. The bath temperature
was maintained up to 40 min and thereafter the solution was kept
at room temperature. After 24 h of deposition, films were taken out
from the beaker, washed using distilled water and thereafter dried
in air. Applying similar process, 0.10 M Cr-doped films were syn-
thesised by using 0.10 M solution instead of 0.05 M solution of CrO3 .
The deposited films were yellowish in colour with good adherent
quality. The films corresponding to the 0.05 and 0.10 M Cr-doped
samples are labelled as ZnS:Cr-I and ZnS:Cr-II respectively.
It is noteworthy to mention that the glass substrates were
chemically cleaned by a mixture of concentrated nitric acid and
iso-propyl alcohol of equal proportion. The glass substrates were
thereafter washed using distilled water and dried in a muffle fur-
nace at 60 ◦ C.
2.2. Characterisation and other measurements
Sample characterisation is an important part of material
research. The structural properties of the films were studied
using X-ray diffraction (XRD) spectra recorded by a diffractome-
ter (SEIFERT, 3003 TT, Germany). The surface morphology of the
films was studied using Atomic Force Microscopy (AFM) (NT-
MDT, NTEGRA Prima, Russia) and Field Emission-Scanning Electron
Microscopy (FESEM) (ZEISS SIGMA VP, Germany). To obtain the
optical band gap, absorption spectra of the films were recorded
using a UV–vis Spectrometer (CARY-300, Varian, Australia). The
current-voltage (I–V) characteristic of the films was recorded by
a digital electrometer (Keithley, 6517B, United States). Aluminium
was used as a connecting electrode and the potential was applied
by a variable DC power supply. The same experimental setup as
reported in Sarma et al. [6] was used for the X-ray radiation sensitiv-
ity analysis. Unless otherwise stated the X-ray source was operated
at 35 kV and 15 mA filament current. The source emits X-ray of
wavelength 1.5406 Å. The X-ray is allowed to fall perpendicularly
on the surface of the film and the distance between the source and
the film was kept constant at 5 cm throughout the experiment.
3. Results and discussion
3.1. Characterisation reports
For structural analysis, XRD patterns of the films were recorded
between 20 and 70◦ at a resolution of 0.05◦ (in 2␪ scale). Fig. 1 shows
the XRD patterns of ZnS:Cr-I and ZnS:Cr-II films. For comparison,
the same feature of an un-doped film is also shown in Fig. 1. The
XRD patterns indicate that the prepared films are polycrystalline
in nature. Comparing the XRD patterns with the joint committee
of powder diffraction standard (JCPDS) data file 05-0566, the peaks
have been indexed as (111), (200), (220), (311) and (400). According
to the indexing, the (111) peak is the most intense one. It is evident
that no additional diffraction peak is observed after doping. How-
ever, the peaks are found to shift towards higher diffraction angle.
The insets in Fig. 1 exemplifies the shifting of (111), (200), (220) and
(311) peaks. This shift may be attributed to the presence of residual
stress in different positions of the films [11] as well as due to the
presence of the Cr impurity. The average crystallite size was esti-
mated using the Scherrer’s equation [12]. For ZnS:Cr-I and ZnS:Cr-II
films, it is estimated as 28.9 and 30.2 nm respectively. In contrast,
the average crystallite size of the un-doped film was 26.3 nm [6].
It implies that the average crystallite size increased with doping as
well as with the doping concentration.
The total broadening of X-ray diffraction peaks occurs due to the
geminate contribution of crystallite size and microstrain. Taking
the influence of microstrain into account, the Williamson-Hall (W-
H) analysis [13] has been carried out and the average crystallite
size is calculated. According to the theory of Williamson-Hall, the
relation between the broadening of a multiple ordered diffraction
330 M.P. Sarma et al. / Sensors and Actuators A 276 (2018) 328–334

Fig. 2. AFM images of ZnS:Cr-II film (a,b) and ZnS film (c,d). Here (a) and (c) show 2D images whereas (b) and (d) show 3D images of the films. The FE-SEM images of ZnS:Cr-II
film (e) and ZnS film (f).

peak having full width at half maxima, ˇ and the crystallite size, D
is


ˇ= + 4 εtan (1)
Dcos

where  is the wavelength of X-ray,  is the diffraction angle and ε

is the microstrain present in the crystal lattice of the films. A plot
of (ˇcos)/ versus 2sin/ yields a straight line with an intercept
equal to 1/D and slope 2ε. This analysis gives the average crys-
tallite size for ZnS:Cr-I and ZnS:Cr-II films as 31.1 and 32.7 nm
respectively. In comparison, the corresponding value for the un-
doped film was 29.1 nm [6]. Further, the microstrain in ZnS:Cr-I
and ZnS:Cr-II films have been calculated as 0.132 × 10−3 and
0.178 × 10−3 whereas that for the un-doped film was 0.136 × 10–3
[6]. The microstrain in the films is found to increase with doping.
Due to the influence of microstrain, the average crystallite size esti-
mated from the W-H plot is found to be slightly higher than that
calculated from the Scherrer’s equation.
To study the surface morphology AFM and FESEM analyses were
carried out. Fig. 2(a,b) show AFM image of ZnS:Cr-II film whereas
Fig. 2(c,d) show the same feature of an un-doped film. The surface
of the films are rough, however, the degree of roughness seems to
increase after doping. The grains having different shape and size are
much visible in the doped film compared to that of in the un-doped
one. Using the WSxM 4.0 Beta7.0 software [14], the root-mean-
square (rms) roughness of the films has been calculated. The rms
roughness of ZnS:Cr-I and ZnS:Cr-II films are found to be ∼200 nm
and 210 nm respectively. In comparison, the rms roughness of the
un-doped film was estimated as ∼178 nm only. It confirms that the
roughness of the films increases after doping. The FESEM images of
ZnS:Cr-II film and the un-doped film are shown in Fig. 2(e) and (f)
respectively. Both films have grains of hexagonal rod-like structure.
Agglomeration of some smaller sized grains is also observed. Inter-
estingly, no significant surface morphological changes have been
observed after doping.
Fig. 3. EDXS spectrum of ZnS:Cr-I film.
For elemental analysis, an EDXS analysis has been carried out.
Fig. 3 shows an EDX spectrum of ZnS:Cr-I film. The spectrum shows
peaks corresponding to Zn, S and Cr. In addition, the spectrum also
consists peaks corresponding to Si, O and C. The presence of Cr indi-
cates the incorporation of Cr atom in the ZnS matrix. On the other
hand, the presence of additional elements (Si, O and C) are might
by from the glass substrate and the substrate holder used in the
EDXS measurement. It is also noteworthy to mention that during
synthesis, the pH was maintained within 9–10 to maintain the con-
centration of OH− ions which plays a major role in the formation of
the films. Therefore, the presence of oxygen in the films is obvious.
Moreover, the contamination of oxygen may also occur due to the
atmospheric air.
3.2. Optical properties
Un-doped ZnS film shows sharp absorbance edge at UV region
due to near band absorption. This absorbance edge usually shifts
after doping of some impurity. To study the absorbance edge and
hence to calculate the optical band gap of the doped films, UV–vis
 M.P. Sarma et al. / Sensors and Actuators A 276 (2018) 328–334
Fig. 4. UV–vis absorbance spectra of ZnS, ZnS:Cr-I and ZnS:Cr-II films. The inset
shows the Tauc’s plot corresponding to the absorbance spectra of ZnS, ZnS:Cr-I and
ZnS:Cr-II films.
Fig. 5. I–V characteristics of ZnS, ZnS:Cr-I and ZnS:Cr-II films recorded under dark
condition (open symbols) and under X-ray radiation (solid symbols).
absorption spectra of the films were recorded. Fig. 4 shows the
absorbance spectra of ZnS:Cr-I and ZnS:Cr-II films. For ease of com-
parison, the same feature of the un-doped film is also shown. It has
been observed that the absorbance edge of the doped films shifts to
higher wavelength side than that of the un-doped film. Moreover,
it is also observed that the magnitudes of absorbance in the doped
films are higher than that of the un-doped film. It is due to the pres-
ence of extra states those created by the Cr impurity in the doped
films which absorb more photon energy than that of the un-doped
film.
The band gap of the films is estimated from the Tauc plot [15].
The Tauc plots corresponding to the un-doped and doped films are
shown in the inset of Fig. 4. For the un-doped film, the optical band
gap is estimated as 3.38 eV [6] whereas that of ZnS:Cr-I and ZnS:Cr-
II films are estimated as 3.25 and 3.23 eV respectively. The band gap
is found to decrease after doping of Cr. This decrease is attributed to
the extra electronic states associated with the Cr located below the
conduction band. Chalcogenide materials contain a large number of
unsaturated bonds or defects those are responsible for the forma-
tion of localized states in the band gap [16]. The unsaturated defects
in the ZnS films may increase with the concentration of Cr. Thus, it
increases the density of localized states in the band structure and
eventually the band gap decreases with the doping concentration.
3.3. Electrical properties
Fig. 5 shows current-voltage (I–V) characteristics of ZnS:Cr-I and
ZnS:Cr-II films recorded under dark condition and under X-ray
radiation. The experimental setup for these measurements was
reported in Sarma et al [6]. For comparison, the I–V characteris-
tics of an un-doped film recorded under the same conditions are
also shown in Fig. 5. Each data point is the average of three identi-
331
cal measurements and the corresponding error bars represent their
standard deviations. For all cases, the current is found to increase
linearly with applied voltage. For the un-doped film, the minimum
voltage for a start-up current under dark condition is 0.50 V whereas
that under the X-ray irradiation is 0.03 V. In contrast, for the doped
films, the minimum voltage for the start-up current under dark con-
dition is 0.10 V whereas that under the X-ray irradiation is only
0.02 V. These imply that the doped films are able to flow current
at relatively lower voltage than the un-doped one. Moreover, in
any conditions, the magnitude of the start-up currents in the doped
films are much higher than the un-doped film. Thus, two impor-
tant scenarios can be observed in Fig. 5: (i) under dark condition,
the current through the doped films is significantly higher than that
of the un-doped film. In addition, the current through ZnS:Cr-II film
is higher than that through ZnS:Cr-I film. (ii) For any films, the cur-
rent under X-ray radiation is significantly higher than that under
the dark condition.
The room temperature electrical conductivity of the films has
been calculated from the I–V characteristics. Under dark condition,
the conductivity of ZnS:Cr-I and ZnS:Cr-II films are calculated as
9.34 × 10−6 and 1.42 × 10–5 S/cm respectively. In comparison, the
conductivity of the un-doped film was 2.06 × 10−6 S/cm [6]. There-
fore, the first scenario implies that the conductivity of the films after
doping increase approximately one order of magnitude. In addition,
the conductivity of the films also increase with doping concentra-
tion. This enhancement of the conductivity in the doped films can
be attributed to different factors such as structural modifications,
decrease of band gap with doping concentration etc. Apart from
these, the presence of each trivalent Cr offers an excess electron
in the ZnS matrix. This excess electron plays the major role in the
enhancement of conductivity of the films.
To explain the second scenario, the electrical conductivity of
the films under X-ray irradiation has been calculated. The conduc-
tivity of ZnS:Cr-I and ZnS:Cr-II films under X-ray irradiation are
found to be 1.55 × 10−4 and 2.16 × 10−4 S/cm respectively. In con-
trast, the conductivity of the un-doped film under X-ray irradiation
was 4.13 × 10−5 S/cm [6]. These show that the conductivity of the
doped films under X-ray irradiation is about one order of magni-
tude higher than that under the dark condition. This is similar to
the un-doped film as well [6]. Thus, the conclusion of the second
scenario is that the conductivity of the films under X-ray irradiation
is higher than the dark condition. It means the doped films respond
to the X-ray radiation in a manner similar to the un-doped film as
reported earlier [6].
To explain the enhancement of conductivity under X-ray radi-
ation, Sarma et al. [6] proposed an energy band model for the
un-doped film. The same model can also be used to explain the
conductivity of the doped films. According to the model, when a
film is exposed to the X-ray radiation, a significant number of elec-
trons excited to the conduction band compare to that under the
dark condition. As a result, the current and hence the conductivity
of the film increases under X-ray radiation. The excitation of elec-
trons under the X-ray radiation depends on the applied voltage,
energy of the incident radiation and band gap of the material [6].
3.4. X-ray detection sensitivity
In the preceding section, it has been observed that the conduc-
tivity of the films under X-ray irradiation condition is significantly
higher than the dark condition. Based on this behaviour, the X-ray
radiation detection sensitivity of the films has been studied as a
function of the voltage applied across the films. For this analysis,
the detection sensitivity (more precisely, the signal-to-noise ratio)
at a particular energy of X-ray radiation has been calculated as
S (V ) = (I r − Id )/Id (2)
332 M.P. Sarma et al. / Sensors and Actuators A 276 (2018) 328–334
Fig. 6. Variation of X-ray radiation detection sensitivity as a function of voltage
applied across the films.
where Ir and Id are the currents under X-ray radiation and under
dark condition respectively. As the X-ray was incident perpendic-
ularly on the surface of the film and the distance between the
source and the film was kept constant throughout the experiment,
therefore, any dependence of the angle of incidence of X-ray and
distance between the source and the film on detection sensitivity
was excluded from Eq. (2). Fig. 6 shows a variation of sensitivity of
ZnS:Cr-I and ZnS:Cr-II films with applied voltage. For ease of com-
parison, the same feature of the un-doped film is also shown. It
has been observed that the sensitivity of the doped films decreases
monotonically with voltage. In particular, the overall decrease of
sensitivity of ZnS:Cr-I film is found to be higher than that of ZnS:Cr-
II film. In comparison to the doped films, the sensitivity of the
un-doped film was constant within 0.50–6.00 V and decreased
thereafter. Although the detection sensitivity of the Cr doped films
decreases with voltage, in Fig. 6, it is evident that the sensitivity of
the doped and un-doped films are approximately constant within
0.50–1.00 V. Above 1.00 V, the sensitivity of both the doped films
decreases almost in a similar way. This behaviour of the doped
films is similar as that of an un-doped TiO2 film whose band gap
is ∼3.26 eV [17], comparable to that of the Cr doped films. The
detection sensitivity of the un-doped TiO2 film is constant between
0.2–3.0 V and decreases with further increase in voltage [17]. The
difference in the variation of sensitivity between the doped and un-
doped films are probably due to the shrinkage of band gap as well
as some structural and surface morphological changes caused by
the Cr impurity.
For the un-doped film, Sarma et al. [6] already discussed the
decrease of sensitivity with voltage. The decrease in sensitivity is
due to the competition of the electrons excited by the applied volt-
age and X-ray radiation. At lower voltages, the number of electrons
excited to the conduction band by X-ray radiation is significantly
higher than those excited by the voltage applied across the film. As
a result, the detection sensitivity of the film is high. On the other
hand, at relatively higher bias voltages, the number of electrons
excited to the conduction band by X-ray radiation become less sig-
nificant compared to those excited by the voltage. Consequently,
the detection sensitivity of the film decreases with increase in volt-
age [6]. Although the decreases of detection sensitivity of the doped
films are found to be higher than the un-doped one but for a partic-
ular voltage, the magnitude of the current through the doped film
will be higher than the un-doped one. Therefore, by doping of Cr in
ZnS, the problem associated with ZnS film for the development of
a low-cost X-ray sensor could be resolved to a significant extent.
The detection sensitivity of the films has been further studied
by changing the energy of X-ray radiation. In this experiment, the
voltage applied across the films was kept constant and the energy
of the X-ray varied by changing the X-ray source potential between
25 and 35 kV while keeping the filament current constant at 15 mA.
Fig. 7. Variation of current flowing through the films as a function of X-ray source
potential corresponding to the voltage of (a) 1.00 V, (b) 3.00 V and (c) 5.00 V applied
across the films. The variation of detection sensitivity of the films as a function X-ray
source potential corresponding to the voltage of (d) 1.00 V, (e) 3.00 V and (f) 5.00 V
applied across the films.
As discussed earlier, the detection sensitivity of the films is constant
within 0.50–1.00 V and decreased thereafter. Therefore, the exper-
iment was carried out by applying different voltages (V = 1.00, 3.00
and 5.00 V) across the films. Fig. 7(a–c) show the variation of current
through the films as a function of X-ray source potential corre-
sponding to the voltages V = 1.00, 3.00 and 5.00 V applied across
the films. Each data point represents the mean of three identical
measurements and the error bars are their corresponding standard
deviations. For all the films, the current was found to increase with
the X-ray source potential. The currents through the doped films
are significantly higher than that of the un-doped one. To quantify
the rate of increase of current, the slope of the plots have been eval-
uated and reported in Table 1. In Table 1, it can be observed that
for any applied voltages between 1.00 and 5.00 V, the magnitude of
the slopes corresponding to the un-doped film are higher than the
doped ones. Indeed, the magnitude of the slopes decrease with the
doping concentration. For each applied voltage, the detection sen-
sitivity of the films has been calculated as a function of the energy of
X-ray. Fig. 7(d–f) show the variation of detection sensitivity of the
films as a function X-ray source potential. To explain the detection
sensitivity under varying energy of X-ray, the slope of each of the
plots are calculated and reported in Table 1. In Table 1, it is evident
that the magnitude of the slope corresponding to the un-doped
film for any applied voltages between 1.00 and 5.00 V is relatively
higher than the doped films. On the other hand, the detection sen-
sitivity of the films decreases with the voltage applied across the
film. This behaviour is, however, more significant for the doped
films. The bigger value of the slope implies that the rate of increase
of sensitivity per unit change of X-ray energy is the highest for the
un-doped film and the lowest for ZnS:Cr-II film. Therefore, despite
 M.P. Sarma et al. / Sensors and Actuators A 276 (2018) 328–334
Table 1
The slopes of the plots shown in Fig. 7.
Applied voltage (V) ZnS film
1.00 (1.54 ± 0.06)×10−11
3.00 (3.62 ± 0.10)×10−11
5.00 (6.21 ± 0.11)×10−11
1.00 0.77 ± 0.03
3.00 0.60 ± 0.02
5.00 0.61 ± 0.01
Fig. 8. (a) The real-time current as a function of time when the X-ray is ON and
OFF. Here the solid lines through the data points are the experimentally measured
current flowing through the films. The dotted lines represent the dark currents cor-
responding to the voltage of 1.00 V applied across the films. (b) The X-ray radiation
induced currents which are digitally mustered by subtracting the dark currents from
the corresponding experimentally measured currents.
having greater conductivity of the doped films, the un-doped film
is superior to the doped ones for detection of any small change in
X-ray energy. It is an important finding of this study.
3.5. Response time of X-ray detection
One of an essential feature of any detector is that the response
should be quick. In order to study the response time of X-ray detec-
tion, or in short, the X-ray sensing speed of the films, an experiment
was carried out. In this experiment, a voltage of 1.00 V was applied
across the films and X-ray having a constant energy allowed to fall
on the films for 2.00 s. The real-time current flowing through the
films was measured by the electrometer (Keithley, 6517B, United
States). The electrometer was set to collect only 40 data points
at a resolution of 0.12 s/channel as soon as the X-ray fall on the
surface of the films. For each film, the whole experiment was car-
ried out for three times and the average of the three independent
measurements was taken for the analysis.
Fig. 8(a) shows the current as a function of time. Here the solid
lines through the data points are the experimentally measured
current flowing through the films. The dotted lines represent the
dark currents corresponding to the voltage of 1.00 V applied across
the films. Fig. 8(b) shows the X-ray radiation induced currents
which are digitally mustered by subtracting the dark currents from
the corresponding experimentally measured currents. Fig. 8(a,b)
clearly show the rise and decay of the radiation induced currents.
It is evident that the current under X-ray radiation rise very quickly,
reaches a steady state and as soon as the X-ray is switched off, the
current decrease to the dark level current. It is also observed that
the net radiation induced currents increase after doping of Cr (see
Fig. 8(b)).
When X-ray photons fall on the films, electrons from the valence
band excite to the conduction band and electron-hole pairs gen-
333
ZnS:Cr-I film ZnS:C-II film Ref.
(1.43 ± 0.05)×10−11 (1.40 ± 0.03)×10−11 Fig. 7(a)
(2.82 ± 0.15)×10−11 (2.71 ± 0.03)×10−11 Fig. 7(b)
(2.82 ± 0.08)×10−11 (2.56 ± 0.07)×10−11 Fig. 7(c)
0.15 ± 0.01 0.08 ± 0.01 Fig. 7(d)
0.10 ± 0.01 0.06 ± 0.01 Fig. 7(e)
0.05 ± 0.01 0.03 ± 0.01 Fig. 7(f)
erate. Due to the applied voltage, the conduction electrons drift
through the external circuit and produce the radiation induced
current. It is reported that in pollycrystalline thin films, there
may be built in potential barriers at the grain boundaries [18].
In such case, a part of the photo-generated charge carriers may
recombine with their respective opposite charges confined at the
depletion region of the grain boundaries and eventually reduce
the potential barriers of the grain boundaries. On the other hand,
the remaining part of the photo-generated charge carriers take
part in the conduction process. The reduction of potential barri-
ers enhances the effective mobility of the charge carriers. As a
result, conductivity of the sample increases. In the present case,
it can be considered that the increase in radiation induced cur-
rents is mainly due to the resultant increase in the X-ray generated
charge carriers and enhancement of their effective mobility. As
soon as the X-ray falls on the films, the number of X-ray gen-
erated charge carriers increase rapidly. However, as the time
elapses, the concentration of the X-ray generated charge carri-
ers reaches a saturation state and causes a constant radiation
induced current through the external circuit. When the X-ray is
switched off, a fraction of conduction electrons recombines with
the holes whereas the remaining part of the conduction elec-
trons drift through the external circuit due to the influence voltage
applied across the films. As no more charge carriers are excited
to the conduction band, the concentration of conduction electron
reduces and thus the radiation induced current falls to the dark
level.
The rise and decay times of the radiation induced current cor-
responding to the doped and un-doped films have been calculated
by drawing two tangents on the rise and decay parts of the plots
(in Fig. 8(b)). For ZnS film, the rise and decay times are estimated as
0.87 s and 1.61 s respectively. In contrast, the rise and decay times of
ZnS:Cr-I film are estimated as 0.83 s and 1.65 s respectively whereas
those of ZnS:Cr-II films are found as 0.80 s and 1.67 s respectively.
This implies that the rise time in any film is shorter than the decay
time. The rise time in ZnS:Cr-II film is the shortest whereas the
decay time is the longest. On the other hand, the rise time in ZnS
is the longest whereas the decay time is the shortest. In ZnS:Cr-II,
the concentration of doping is high. Therefore, under X-ray radia-
tion, the trivalent Cr impurity offers more excess electrons in the
ZnS matrix and thereby causes more electron-hole pairs to form.
Some of these radiation induced charge carriers recombine with
their respective opposite charges confined at the depletion region
of the grain boundaries and thereby reduce the potential barriers of
the grain boundaries. The reduction of potential barriers enhances
the effective mobility of the charge carriers. Due to the enhance-
ment of charge mobility, the electrons take less time to reach the
saturation state and thus cause the shortest rise time in ZnS:Cr-II
film. On the other hand, owing to the greater concentration of Cr
in ZnS:Cr-II film, the number of electrons at the conduction band
might be higher than the un-doped and ZnS:Cr-I films. Therefore,
when the X-ray is switched off, the conduction electrons take more
time to drift through the external circuit. Thus, the decay time is the
longest in ZnS:Cr-II film. From these analyses, although some dif-
ferences in the rise and decay times have been observed between
the un-doped and doped films but in terms of practical applications,
334 M.P. Sarma et al. / Sensors and Actuators A 276 (2018) 328–334
the magnitude of differences are not too high. It means, in terms of
response speed, the effect of doping is not very significant.
4. Conclusions
In this work, we studied the X-ray radiation detection sensitivity
of Cr doped ZnS thin film synthesised by a CBD technique and pre-
sented a comparative study of the detection sensitivity of Cr doped
film with an un-doped ZnS film. Due to doping of Cr in ZnS, the
XRD peaks shifted towards higher diffraction angle, average crys-
tallite size decreased and microstrain as well as the roughness of the
films increased. In addition, the band gap of the films also decreased
from 3.38 to 3.23 eV. I–V characteristics of the films were studied
under dark condition and under X-ray radiation. Under both dark
and X-ray radiation, the doping of trivalent Cr in ZnS matrix offered
excess electrons in the conduction band and that produced the cur-
rents which was about 10 times higher than the un-doped film.
Regarding the X-ray detection sensitivity, the doped films under the
X-ray radiation produced more current than the un-doped one. This
makes the doped film more useful than the un-doped one. How-
ever, the un-doped film was found to be more effective to detect
any change in energy of the X-ray radiation. Regarding the response
time, the rise time of radiation induced current in the doped film
was found to be shorter than that in the un-doped film whereas
the decay time is found to be longer than that in the un-doped film.
However, in terms of practical application, the magnitude of these
differences between the doped and un-doped films are not very
significant. In other words, it can be concluded that the effect of
doping on the response time of X-ray detection is negligibly small.
However, as the conductivity of the doped film is found to be higher
than the un-doped one, so the doped film gives a greater output cur-
rent than the un-doped one. Therefore, the Cr doped ZnS film could
be more useful for the development of low-cost X-ray sensor.
Acknowledgments
Authors thank with gratitude the Department of Physics, IIT,
Guwahati for providing the XRD facility and the Institute of Advance
Studies in Science and Technology (IASST) Boragaon, Guwahati for
giving the AFM, FESEM and EDXS reports.
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Biographies
M.P. Sarma is currently a Ph.D. research scholar in
the Department of Physics, Cotton University (registered
under Gauhati University), India. His research interest is
synthesis and application of thin film. He completed his
Master in Science (M.Sc.) degree in Physics from Gauhati
University, India in 2011. The areas of specialization in
M.Sc. were Condensed Matter Physics, Nanoscience &
Technology and Electronics.
Dr. J.M. Kalita received his Master of Science degree in
Physics in 2011 and PhD in Physics in 2015 from the
Gauhati University of India. His PhD thesis focused on the
stimulated luminescence properties of some natural min-
erals and their application in radiation dosimetry. After
completion of his PhD, in June 2016 he joined the Lumines-
cence Research Laboratory of the Department of Physics
and Electronics, Rhodes University as a Post-doctoral Fel-
low. He is studying the luminescence properties of some
high sensitivity radiation dosimeters using various stim-
ulated luminescence techniques. In addition, he is also
working in the field of thin film deposition and their appli-
cation in high-energy radiation sensor.
Dr. G. Wary is an Associate Professor of Physics, Cotton
University, Guwahati (India). His areas of research inter-
est are (a) thin semiconducting films & their applications
and (b) themoluminescence properties of some natural
minerals in material sciences. Presently he has entrusted
working in the high-energy radiation sensor materials. He
has published more than 50 research papers.