Journal of Saudi Chemical Society (2014) 18, 327–339

King Saud University

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ORIGINAL ARTICLE

Structural, morphological and optical studies on

chemically deposited nanocrystalline CdZnSe thin
films
Soumya R. Deo a, Ajaya K. Singh b,*, Lata Deshmukh a, L.J. Paliwal c,
R.S. Singh d, Rameshwar Adhikari e

a
Dr. Ira Nimdeokar P.G. & Research Centre for Chemistry, Dept. of Chemistry, Hislop College, Nagpur 440002, India
b
Dept. of Chemistry, Govt. V.Y.T.P.G. Autonomous College, Durg 491001, India
c
Dept. of Chemistry, Rashtrasant Tukadoji Maharaj Nagpur University, Nagpur 440002, India
d
Dept. of Physics, Govt. Daanveer Tularam College, Utai, Durg 491107, India
e
Central Department of Chemistry, Tribhuvan University, Kathmandu, Nepal

Received 2 November 2013; revised 16 January 2014; accepted 20 January 2014

Available online 12 February 2014

KEYWORDS Abstract In the present paper, cadmium zinc selenide (Cd0.5Zn0.5Se) thin films were deposited on
Cadmium zinc selenide; glass substrates by chemical bath deposition with optimized deposition parameters. 2-mercap-
2-ME; toethanol was used as a capping agent. The as-deposited thin films were annealed at 300, 500
XRD; and 700 C and then subjected to various structural, morphological and optical investigations.
SEM; The effect of the presence of capping agent and annealing on these properties was discussed. The
Annealing; phenomenon of phase transformation occurred during annealing. The optical band gap energies
Optical properties were found in the range 2.37–1.7 eV with respect to the annealing temperatures.
ª 2014 King Saud University. Production and hosting by Elsevier B.V. Open access under CC BY-NC-ND
license.

1. Introduction transistors [3], photoelectrodes [4], light emitting diodes [5,6],

The wide band gap II–VI CdSe and CdSe type semiconductor
thin films have been attracting considerable attention during
the last few decades due to their wide applications in various
opto-electronic technologies such as lasers [1], sensors [2],
* Corresponding author. Tel.: +91 9406207592.
E-mail address: ajayaksingh_au@yahoo.co.in (A.K. Singh).
Peer review under responsibility of King Saud University.
Production and hosting by Elsevier
photocatalysts [7], optical wave guides [8], and solar cells
[9–13]. More recently, nanosize-structures have gained a much
interest due to their structural, morphological and optical
properties for their potential use in various technological
purposes. Cadmium zinc selenide (CdZnSe), one of the II–VI
group semiconductor materials, plays a prominent part in
the modern material science and technology. CdZnSe is an
n-type semiconductor material and has interesting size
dependent properties as well as high stability and wide band
gap which covers the maximum electromagnetic spectrum [14].
The thin films of CdZnSe have been prepared by molecular
beam epitaxy (MBE) [15], vacuum evaporation [16], electrode-

1319-6103 ª 2014 King Saud University. Production and hosting by Elsevier B.V. Open access under CC BY-NC-ND license.
http://dx.doi.org/10.1016/j.jscs.2014.01.005
328
position [17], electron beam pumping [18], chemical bath
deposition (CBD) [19–24] etc. Among the above mentioned
deposition techniques, CBD often appears as the most
attracting and convenient technique due to its low cost and
remarkable ability to produce thin films with comparable
quality to those thin films which are produced by other expen-
sive and sophisticated deposition techniques. In the present pa-
per, we report the deposition of Cd0.5Zn0.5Se thin films on
glass substrates by CBD technique to study their structural,
morphological and optical properties and the effect of annealing
at various temperatures on these properties is also discussed.
2. Experimental details
2.1. Materials
Cadmium acetate dihydrate [Cd(CH3COO)2.2H2O], zinc ace-
tate dihydrate [Zn(CH3COO)2.2H2O], cadmium chloride
(CdCl2.H2O), sodium sulfite (Na2SO3), elemental selenium
powder (99.9%) 2-mercaptoethanol (2-ME), and triethanola-
mine (TEA) were obtained from Merck, Mumbai, India and
30% ammonia solution was purchased from S D Fine-Chem
Limited, Mumbai, India. All reagents used were of AR grade.
Deionized water was used to prepare precursor solutions. All
reagents were used as received without any further purification.
Commercially available microscopic glass slides (Blue Star, Po-
lar Industrial Corporation, Mumbai, India) with the dimension
of 75 mm · 25 mm · 2 mm were used as glass substrates.
2.2. Preparation of Cd0.5Zn0.5Se thin films
The thin films of Cd0.5Zn0.5Se were prepared by CBD tech-
nique on commercially available microscopic glass slides. To
prepare Cd0.5Zn0.5Se thin films, 7.5 mL of 1 M cadmium ace-
tate and 7.5 mL of 1 M zinc acetate solutions were taken in
a beaker of 100 mL volume and magnetically stirred for few
minutes. 5 mL of TEA was added to this mixture with contin-
uous stirring. On addition of TEA, it was found that the color
of the mixture turned milky. Then, 15 mL of 30% ammonia
solution was added slowly with constant stirring and the milky
Figure 1 Cd0.5Zn0.5Se thin films: (a) as-deposited; (b) capped with 2-ME and (c)–(e) annealed (at 300, 500 and 700 C).
S.R. Deo et al.
solution turned clear. After this, 15 mL of sodium seleno sul-
fate (which was obtained by heating sodium sulfite and ele-
mental selenium powder at stoichiometric amount with
100 mL of deionized water at 90 C for 5 h followed by the fil-
tration of excess selenium), 2 mL of 0.01 M 2-mercaptoethanol
(2-ME, used as capping agent) and 2 mL of 0.01 M cadmium
chloride (used as flux) were added sequentially with constant
stirring. The whole reaction mixture was stirred for few min-
utes. The precleaned glass substrates were then immersed ver-
tically in the beaker containing reaction mixture or bath and
kept at a constant temperature of 70 C in a water bath for
4 h. The pH of reaction bath was 10.5.
After deposition, the substrates were taken out from the
reaction bath and washed with deionized water to remove
loosely attached particles to the substrates and dried in air at
room temperature. The as-deposited thin films were then an-
nealed in air at 300 and 500 C for 10 min and at 700 C for
2 min. Fig. 1 represents the appearance of as-deposited,
capped and annealed (at 300, 500 and 700 C) samples of
Cd0.5Zn0.5Se thin films.
2.3. Characterization of thin films
The structural determination of Cd0.5Zn0.5Se thin films was
carried out by Bruker (D8 Advanced), Germany, X-ray dif-
fractometer in the scanning range 20–80 (2h) using CuKa
radiation with the wavelength of 1.5406 Å and the XRD pat-
terns of these films were recorded at 25 C. The microstructure
and surface morphology of these films were studied by a
JEOL-5600 scanning electron microscope and atomic force
microscope-Nanoscope-E (AFM-NSE) at contact mode using
silicon nitride tip, respectively. The chemical composition anal-
ysis was done by using an INCA EDAX spectrometer, setup
attached with SEM. The FTIR studies were done by a VAR-
IAN Vertex Fourier transform infrared spectrophotometer.
The optical properties were investigated by a VARIAN Cary
50 Bio UV–Visible spectrophotometer and the spectra were
recorded in the wavelength range 350–800 nm. The photolumi-
nescence studies were done by a Perkin-Elmer LS55 lumines-
cence spectrometer.
Studies on chemically deposited nanocrystalline CdZnSe thin films 329

3. Results and discussion

3.1. Deposition of Cd0.5Zn0.5Se thin films

The aqueous solutions of cadmium acetate, zinc acetate and

thiourea were used as the sources of Cd2+, Zn2+ and Se2,
respectively and the reactions are as follows:
Cadmium acetate and zinc acetate dissolve in water and re-
lease Cd2+ and Zn2+ as:
CdðCH3 COOÞ2 ! Cd2þ þ 2CH3 COO ð1Þ

ZnðCH3 COOÞ2 ! Zn2þ þ 2CH3 COO ð2Þ

2+ 2+
The addition of TEA in Cd and Zn salt solution mix-
ture gives a milky colored mixture, is an indication of
Cd2þ þ TEA ! ½CdðTEAÞ2þ ð3Þ

Zn2þ þ TEA ! ½ZnðTEAÞ2þ ð4Þ

2
The Se ions are released due to the hydrolysis of sodium
selenosulfate in the alkaline medium according to the follow-
ing reaction:
Na2 SeSO3 þ OH ! Na2 SO4 þ HSe ð5Þ

HSe þ OH ! Se2 þ H2 O ð6Þ

Addition of ammonia in the mixture, reacts with
[Cd(TEA)]2+ and [Zn(TEA)]2+ and forms [Cd(NH3)4]2+ and
[Zn(NH3)4]2+ complex ions.
½CdðTEAÞ2þ þ 4NH3 ! ½CdðNH3 Þ4 2þ þ TEA ð7Þ

½ZnðTEAÞ2þ þ 4NH3 ! ½ZnðNH3 Þ4 2þ þ TEA ð8Þ

Finally, the deposition of Cd0.5Zn0.5Se film occurs accord-
ing to the following reaction:
2þ
½CdðNH3 Þ4  þ ½ZnðNH3 Þ4 2þ þ Se2
! Cd0:5 Zn0:5 Se þ waste product ð9Þ
The as-deposited thin films were uniform and well adhered
to the substrates. A red colored thin film was deposited on the
substrates. Figure 2 XRD diffraction patterns of Cd0.5Zn0.5Se thin films: (a)
as-deposited; (b) capped with 2-ME and (c)–(e) annealed (at 300,
3.2. XRD studies 500 and 700 C).

The structural determination of Cd0.5Zn0.5Se thin films was

carried out by X-ray diffraction technique and the patterns
for as-deposited, capped and annealed (at 300, 500 and
700 C) thin films are shown in Fig. 2. Fig. 2(a) demonstrates
the XRD pattern for as-deposited Cd0.5Zn0.5Se thin film. The
peak [1 1 1] and [4 0 0] corresponds to the cubic phase of CdSe
whereas the peak [1 0 2] at 2h = 37.5 indicates the hexagonal
phase of ZnSe. While in Fig. 2(b), some peaks appeared more
clearly due to the confinement of Cd0.5Zn0.5Se particles in the
presence of 2-ME as capping agent. This observation con-
firms that the film had polycrystalline nature. Fig. 2(c) repre-
sents the XRD pattern of Cd0.5Zn0.5Se thin film annealed at
300 C. The planes [1 0 0], [0 0 2], [1 0 1], [1 1 0] and [1 0 3]
regarding CdSe and the planes [0 0 2] and [0 0 4] regarding
ZnSe indicate the hexagonal structure of the material, while
a small peak at 2h = 62.41 exhibits that a small amount of
CdSe exists in the cubic form, which gets vanished at higher
annealing temperature of 500 and 700 C, strong evidence of
phase transformation from meta-stable cubic to stable hexag-
onal structure. It has also been reported earlier that the cu-
bic-to-hexagonal phase transformation occurred at above
250 C in the case of chalcogenide materials [25,26]. The pres-
ence of high intense and sharp peaks in Fig 2(d) and (e)
exhibited improved crystallinity of the films and appearance
of some extra peaks is due to the reorientation of the nano-
crystals after annealing at higher temperature. Any peak cor-
responding to metal or chalcogenide oxide was not obtained
during annealing, because at higher annealing temperature
(i.e. 700 C), the thin film sample was annealed for limited
time of 2 min. All the structural parameters were calculated
and presented in the Table 1.
330 S.R. Deo et al.

Table 1 Structural parameters for Cd0.5Zn0.5Se thin films.

Material Depo. 2h (deg.) hkl Lattice spacing Grain size Disloc. density Micro strain Lattice parameter
Temp. (K) ‘d’ (Å) ‘D’ (nm) d · 1016 e · 103
2 a c
lines/m
Cd0.5Zn0.5Se (uncapped) 343 25.75 1 1 1(C) 3.38 7.68 16.43 6.98 6.29 –
Cd0.5Zn0.5Se (capped) 26.12 1 1 1(C) 3.45 4.21 37.08 24.51 6.38 –
Cd0.5Zn0.5Se (annealed at 300 C) 26.48 0 0 2(H) 3.41 6.97 11.24 13.03 – 4.53
Cd0.5Zn0.5Se (annealed at 500 C) 26.66 0 0 2(H) 3.36 8.12 7.44 9.96 – 4.41
Cd0.5Zn0.5Se (annealed at 700 C) 26.72 0 0 2(H) 3.22 10.53 4.83 7.21 – 4.32

Figure 3 SEM images of Cd0.5Zn0.5Se thin films: (a) as-deposited; (b) capped with 2-ME and (c)–(e) annealed (at 300, 500 and 700 C).

3.3. SEM studies 3.4. AFM studies

In order to study the microstructures of Cd0.5Zn0.5Se thin
films, scanning electron microscopy (SEM) was used. Fig. 3
shows the SEM images of as-deposited, capped and annealed
(at 300, 500 and 700 C) thin films. In Fig. 3(a) and (b), spher-
ical shaped nanoparticles with vacant spaces were observed,
while on annealing, the film consists of dense layer of small
crystallites and the nanoparticles convert into bigger clusters
due to the coalescence or diffusion of large number of
Cd0.5Zn0.5Se nanoparticles which can be seen in Fig. 3(c)–(e).
The distribution of nanoparticles becomes more ordered
and the vacant spaces between them get occupied. This can
be explained as during the annealing, the recrystallization
process densified the film and eliminated the defects in the
material.
The surface morphology of Cd0.5Zn0.5Se thin films was studied
by atomic force microscopy (AFM). Fig. 4(a)–(e) show the sur-
face images of Cd0.5Zn0.5Se of as-deposited, capped and an-
nealed (at 300, 500 and 700 C) thin films. From Fig. 3(a)
and (b), it was observed that the films had some voids and
cracks, which can be seen clearly. After annealing, it was found
that all the defects get eliminated [as shown in Fig. 3(c)–(e)]. It
was also observed that the particle sizes on the surface of
CdZnSe film increased as the annealing temperature increased.
It can be attributed to the agglomeration of particles on the
surface of the prepared thin films. This indicates the improve-
ment of crystallinity of the films during annealing. From the
images, it is clear that the film is uniform and the surface of
substrate is well covered by spherical or elliptical particles.
Studies on chemically deposited nanocrystalline CdZnSe thin films 331

Figure 4 AFM images of Cd0.5Zn0.5Se (a) as-deposited; (b) capped with 2-ME and (c)–(e) annealed (at 300, 500 and 700 C) thin films.

Figure 5a EDX pattern for Cd0.5Zn0.5Se thin film.

3.5. EDX studies

The chemical composition analysis was carried out on Cd0.5-

Zn0.5Se thin film sample by energy dispersive X-ray (EDX)
analysis. Fig. 5(a) shows the representative EDX pattern of
Cd0.5Zn0.5Se thin film which confirms the formation of Cd0.5-
Zn0.5Se alloy and also confirms the presence of cadmium, zinc
and selenium. An intense peak for selenium was found in the
spectrum due to its higher concentration as in comparison to
cadmium and zinc. Fig. 5(b) represents the atomic percentage
of the elements present in the thin film sample.
Figure 5b Atomic percentage of constituent elements in Cd0.5-
3.6. FTIR studies Zn0.5Se thin film.

Fig. 6(a) shows the FTIR spectra for 2-ME capped Cd0.5Zn0.5-
Se thin film. The data is summarized in Table 2, from which it
was observed that the bands corresponding to –CH2 vibra-
tions, both symmetric and asymmetric, of 2-ME bound Cd0.5-
Zn0.5Se nanoparticles were obtained at 2862 cm1 and
2913 cm1, respectively. –OH stretching and –CH2 bending
vibrations in the range 3302 and 1495 cm1, respectively, were
observed in the spectra. This observation suggests that the –
OH group is free and not involved in the adsorption [as shown
332 S.R. Deo et al.

Figure 6a FTIR spectrum of 2-ME capped Cd0.5Zn0.5Se thin film.

Table 2 FTIR band positions of 2-ME capped Cd0.5Zn0.5Se thin films with their assignments.
Assignments Band position of 2-ME capped Cd0.5Zn0.5Se thin films (in cm1)

OH group 3302
Symmetric and asymmetric stretching in CH2 vibrations of alkyl chain 2862, 2913
–CH2 bending 1495
–CH2 wagging 1373
–CH2 rocking 1153
C–H deformation (out of plane) 1003
C–S stretching 631

Figure 7a Optical absorption spectra of Cd0.5Zn0.5Se as-depos-

ited, capped with 2-ME and annealed (at 300, 500 and 700 C) thin
Figure 6b A diagrammatic representation for 2-ME capped
films.
Cd0.5Zn0.5Se nanoparticle based on FTIR result.
Studies on chemically deposited nanocrystalline CdZnSe thin films 333

in Fig. 6(b)]. The absence of distinct peak regarding the –SH

stretching can be described as the cleavage of S–H bond and
the formation of new bond (i.e. S-Cd0.5Zn0.5Se nanoparticle).
The singlet at 631 cm1 for bound 2-ME belongs to C–S
stretching band. While, the singlets at 1373 and 1153 cm1
can be attributed as –CH2 wagging and –CH2 rocking
vibrations, respectively.

3.7. UV–Visible absorption studies

Fig. 7(a) shows a complex UV–visible absorption spectra of as-

deposited, capped and annealed (at 300, 500 and 700 C)
Cd0.5Zn0.5Se thin film samples. The optical absorption mea-
surements were performed at room temperature and the opti-
cal spectra of thin films were recorded in the wavelength range
350–800 nm. The as-deposited Cd0.5Zn0.5Se thin film showed
an absorption edge at 460 nm, while an absorption edge for
Figure 7b Plot of (ahm)2 v/s hm of as-deposited, capped and
2-ME capped thin film was found blue shifted (414 nm) due
annealed (at 300, 500 and 700 C) Cd0.5Zn0.5Se thin films.
to the quantum confinement effect (QCE) [27,28]. This phe-
nomenon strongly occurred when the radius of nanoparticles
is lower than or comparable to Bohr exciton radius [29] and
strongly affects the surface structure and nanoparticle size. Table 3 Estimated band gap values for Cd0.5Zn0.5Se as-
In that case, the charge carriers i.e. electrons, holes and exci- deposited, capped (with 2-ME) and annealed (at 300, 500 and
tons, have confined space for their motion in three spatial 700 C) thin film samples.
dimensions and this effect is followed by the quantization of Material Band gap (eV)
energy level [30,31] results in the increasing band gap [32].
Cd0.5Zn0.5Se (as-deposited) 2.20
The absorption edge of Cd0.5Zn0.5Se thin film was shifted
Cd0.5Zn0.5Se (capped with 2-ME) 2.37
toward the higher wavelengths (i.e. red shift) with increasing Cd0.5Zn0.5Se (annealed at 300 C) 2.17
annealing temperature, which exhibited the phenomenon of Cd0.5Zn0.5Se (annealed at 500 C) 1.91
phase transformation [33,34]. According to a careful observa- Cd0.5Zn0.5Se (annealed at 700 C) 1.7
tion of the absorption spectra, it was found that as the anneal-
ing temperature increased, the hexagonal phase dominates the
structure. Such type of phase transformation occurred due to
change in atomic configuration as the smaller particles fused
into bigger crystallites or clusters. As the annealing tempera-
ture increased, the crystallite size of CdZnSe thin film was also
increased resulting in a shift of absorption edge toward higher
wavelength side (i.e. red shift of absorption edge). The optical
absorption studies revealed that the films are highly absorptive
and have direct type of transitions, which allowed the
determination of optical band gap by the following Tauc’s
relationship:
a ¼ A½hm  Eg 1=2 =hm
where, a is the absorption coefficient, A is a constant and hm is
the radiation energy.
The extrapolation of a plot between (ahm)2 v/s hm [refer
Fig. 7(b)] gives the value of band gaps ‘Eg’ for Cd0.5Zn0.5Se
as-deposited, capped and annealed (at 300, 500 and 700 C) Figure 8 Photoluminescence spectra for capped and annealed (at
thin films, which are in the range 2.37–1.7 eV, given in Table 3. 300 and 500 C) Cd0.5Zn0.5Se thin films.

3.8. Photoluminescence studies

The photoluminescence (PL) studies of Cd0.5Zn0.5Se thin films
were carried out at room temperature and the excitation wave-
length was 375 nm. Fig. 8 shows the PL emission spectra for
Cd0.5Zn0.5Se capped and annealed (at 300 and 500 C) thin
films. The PL spectra for all the samples show a single peak.
The peak regarding 2-ME capped Cd0.5Zn0.5Se thin film sam-
ple was obtained at lower wavelength (at 458 nm). From the
spectra, it was observed that the PL intensity was improved
when the samples were annealed up to 500 C and the peak be-
came more intense from the earlier one due to the enhanced
crystallinity, during annealing [35]. This phenomenon can be
understood on the basis that upon annealing the impurities
were substituted properly and resulted in improved emission
intensity. This study is supported by SEM studies where parti-
cle distribution is homogeneous and free of defects. This type
of enhancement in the emission intensity is due to change in
band gap and increase in particle sizes of the thin film with
 334
Table 4 A comparative study on previously reported methods/techniques and present work.
S. No. Method/technique Material Precursors Depo. Temp. Form Remarks Refs.
1 (a) Molecular beam Zn0.5Cd0.5Se Evaporated 10 K to room Thin films, grown on Energy gap dependence [36]
epitaxy elemental sources of temperature GaAs substrates with temperature was
Cd, Zn and Se influenced by Bose–
Einstein distribution
function; Raman spectra
displayed a typical
multiphonon (MP)
Raman process
(b) CdxZn1xSe Evaporated 553 K Thin films, grown on Increase in Cd content [37]
(x = 0.21,0.23, elemental sources of predeposited ZnSe increased the local
0.35,0.4) Cd, Zn and Se buffer layer over compositional disorder
GaAs substrates as well as increased
planer tensile strength;
partial strain relaxation
occurred due to
interdiffusion process
during the growth
(c) Cd rich (Cd, Zn)Se Evaporated Not mentioned Thin films, grown on Increase in Cd content [38]
quantum dots elemental sources of predeposited ZnSe increased the total
Cd, Zn and Se buffer layer over atomic displacement;
GaAs substrates excitonic gain decreased
due to lack of quantum
dots populated with
excitons
(d) ZnCdSe quantum Evaporated 523 K Thin films, grown on Energy difference [39]
dots elemental sources of predeposited ZnSe became larger due to
Cd, Zn and Se buffer layer over increased Cd
GaAs substrates composition; quantum
dots with higher
emission energies
quenched their signals
due to confinement
related ionization of
quantum dots
(e) Zn1xCdxSe Evaporated Not mentioned Thin films, grown on Roughness increased [40]
elemental sources of GaAs substrates upon increasing the
Cd, Zn and Se value of x; XRD peaks
shifted toward higher 2h
values due to increased
Cd content; grain size
decreased upon

S.R. Deo et al.

increasing Cd content;
crystalline material with
no stacking faults or
twins
 Studies on chemically deposited nanocrystalline CdZnSe thin films
2 Evaporation
(a) Hot wall evaporation ZnxCd1xSe CdSe and ZnSe 900–1000 K Thin films, grown on Columnar grains with rough [41]
(x = 0.09, 0.66, powders (99.999%) glass substrates surface; crystal structure depends
0.91) on the x values; the effect of
mechanical stress in grain
boundary associated with
electrostatic fluctuation
(b) Electron beam evaporation ZnxCd1xSe Elemental Zn 1123–1153 K Thin films, grown on Polycrystalline; cubic structure [42]
(x = 0.10, 0.30, (99.9999%), Cd glass substrates with (1 1 1) plane; showed good
0.05, 0.58, 0.70, (99.9999%) and Se transparency in the wavelength
0.90) (99.99%) region from 1.0 to 2.5 lm; value
of band gap varied from 1.6 to
2.6 eV depending on the value of
x
(c) Thermal evaporation ZnxCd1xSe Elemental Zn (6 N), 1220–1250 K Thin films, grown on In the composition range from [43,44]
(x = 0.2, 0.4, 0.6, Cd (5 N) and Se glass and quartz x = 0 to x < 0.6, films were
0.8) (4 N) substrates found to crystallize in wurtzite
structure, while in the
composition range from x 6 0.6
to x = 1, films were found to
crystallize in sphalerite structure;
absorption edge shifted to
shorter wavelengths as the film
composition parameter x
increased; variation in band gap
energy from 1.79 to 2.38 eV
depending on the value of film
composition parameter x
3 (a) Electrodeposition CdZnSe Na2SeSO3 (as Se Room temperature, Thin films, grown on Presence of cracks and [45]
source), CdCl2 (as annealed at 393 K Titanium sheets characteristic grains on the
Cd source) for 1 h and 773 K surface of unannealed CdZnSe
complexed with for 20 min. film; while the surface became
EDTA, ZnCl2 (as more uniform during annealing;
Zn source) compound plating mechanism of
complexed with CdSe and ZnSe deposition was
NH3 confirmed by voltamperometric
investigations; introduction of Zn
to CdSe improved the power
conversion efficiency
(b) CdZnSe CdSO4.H2O Room temperature Thin films, grown on Polycrystalline; band gaps [46]
(98+%), SeO2 Se deposited Au depend on the film composition
(99.8%), electrode modulated by controlling
ZnSO4.7H2O electrolyte composition; surface
(99%), Na2SO4 of Se deposited Au act asp-type
(99+%), H2SO4 semiconductor during
(98+%) photocorrosion of Se to Se2-;
electrode mass decreases with

335
increased frequency
(continued on next page)
 336
Table 4 continued
S. No. Method/technique Material Precursors Depo. Temp. Form Remarks Refs.
4 Melt cooling Se85Cd15xZnx Se, Cd and Zn in 1173 K Powder Polycrystalline nature with zinc [16,47]
technique (x = 0, 3, 7, 11, 15) elemental form (all blende structure; thermal
99.999% pure) conductivity and diffusivity
increased with increasing Zn
percentage; due to change of
covalent bonding into iono
covalent bonding, binding energy
of the alloy also increased
5 Temperature ZnxCd1xSe CdSe (5 N), ZnSe 1173 K Slices with thickness Polycrystalline nature; hexagonal [48]
Gradient Solution (x = 0.3) (5 N) and Se (6 N) varying from 0.2 to structure with (1 1 2 0) plane; at
Zoning (TGSZ) 2 mm higher temperature, Se vacancies
technique reduced which converted the
materials conductivity into p-
type; resistivity depends on the
energy band gap of the material
6 Screen printing Cd1xZnxSe (x = 0, CdSe (99.999%), Sintered at 723 K for Thin films, printed Direct type transition, band gap [49]
followed by sintering 0.2, 0.4, 0.6, 0.8) ZnSe (99.999%), 10 min. over glass substrates varied from 1.69 to 2.58 eV as the
ZnCl2 (as adhesive), value of x varied from 0 to 1;
Ethylene glycol (as polycrystalline nature with cubic
binder) phase; stable under wide
deviations from the
stoichiometry; conduction
through thermally activated
process
7 Metal–organic Zn0.56Cd0.44Se Zn (CH3)2, 583 K Thin films, grown on Dome shaped islands grown over [50]
chemical vapor Cd(CH3)2, H2Se, GaAs substrates the substrates; growth proceeds
deposition high purity H2 as through layer-by-layer process,
(MOCVD) carrier gas then mass transfer from 2D to
3D dot under Stranski–
Krastanow mode
8 Pulse plating CdxZn1xSe CdSO4, ZnSO4, Room temperature Thin films, grown on Cubic structure with (1 1 1) phase; [51]
(x = 0.1, 0.2, 0.3, SeO2 Titanium and XRD peaks shifted toward CdSe
0.4, 0.5, 0.6, 0.7, 0.8, conducting glass side with increased CdSe content
0.9) substrates in mixture; band gap varied from
1.72 to 2.70 eV with variation of
x; surface roughness became
higher due to larger grain size
9(a) Chemical bath Cd1xZnxSe (x = 0, CdSO4, ZnSO4, 343 ± 2 K Thin films, grown on Polycrystalline nature; have [19]
deposition: Chemo- 0.025, 0.050, 0.075, Na2SeSO3 glass substrates mixed phases; wurtzite
mechanical synthesis 0.1, 0.2, 0.3, 0.4, 0.5, (dominant) in Cd rich films and
0.6, 0.7, 0.8, 0.9, cubic (dominant) in Zn rich films;

S.R. Deo et al.

0.95, 1.0) deposition process based on ion-
by-ion basis on substrates; rough
surface with clearly defined
uniformly distributed grains;
band gap varied from 1.7 to
2.5 eV.
 Studies on chemically deposited nanocrystalline CdZnSe thin films
(b) Cd0.7Zn0.3Se CdCl2, Zn(NO3)2, 343 K, annealed at Thin films, grown on Nanocrysalline nature with [26,52]
Na2SeSO3 473, 573 and 673 K ITO substrates hexagonal structure; tetragonal
phase present at higher annealing
temperature due to formation of
CdIn2Se4; increase in grain size
with increasing annealing
temperature; smooth, uniform,
well adhered to substrates;
absorption edge shifted toward
longer wavelengths with
increasing annealing temperature
band gap varied from 2.08–
1.72 eV with respect to annealing
temperatures.
(c) Cd0.5Zn0.5Se Cd(CH3COO)2. 343 K, annealed at Thin films, grown on Polycrystalline texture; uniform, Present work
2H2O, 573 and 773 (for glass substrates well adhered to substrates; phase
Zn(CH3COO)2 10 min) and at transition occurred above 573 K
.2H2O, Na2SeSO3, 973 K (for 2 min) from cubic to hexagonal
CdCl2.H2O (as flux), structure; crystallinity improved
TEA (as complexing during annealing; stable at higher
agent) annealing temperature; spherical
shaped nanoparticles converted
to bigger cluster during
annealing; highly absorptive and
direct type transition; band gap
varied from 2.37 to 1.7 eV with
respect to annealing temperatures

337
338
increasing annealing temperature. Moreover, no additional
impurity phase was observed for all the samples that indicate
that all the samples were free of impurities. A continuous
increase in the emission intensity of the samples of CdZnSe
thin films capped with 2-ME and annealed at 300 and
500 with increasing annealing temperature may be ascribed
as the enhancement of crystallinity with increased annealing
temperatures.
4. Significance of the work
Today, various application areas are emerging and focusing on
the use of nanoparticles as a technology for the development
and progress of all the spheres of life, i.e. social, industrial
and economical. From the viewpoint of science and technol-
ogy, the main purpose of the preparation of thin films on suit-
able substrates is to design a system for the improvement in the
performance of the devices made up of it. The thin films of
CdZnSe have great importance and significance in a large vari-
ety of industrial applications. Earlier, various workers have re-
ported the synthesis of CdZnSe thin films by a variety of
techniques and extensively studied their structural and optical
properties, which can be seen in Table 4. These thin films can
be used either as the basic material for the fabrication of solar
cells or as the photoelectrodes for the large area deposition of
other semiconducting materials for solar cell purposes. They
can also be used as photocatalysts for the generation of hydro-
gen in the form of fuel used as the alternative source of energy,
by water splitting. Renewable energy sources have a great con-
tribution to create a sustainable energy system. Further re-
search and developments in the applications of CdZnSe thin
films can give a boost to the betterment of this energy system.
5. Conclusion
The thin films of Cd0.5Zn0.5Se were deposited on glass sub-
strates from aqueous alkaline reaction bath by CBD. The
XRD studies showed that the samples were of polycrystalline
in nature, whereas the films annealed above 300 C exhibited
pure hexagonal structural property; and it was found that
the crystalline nature of thin films after annealing became bet-
ter. SEM and AFM studies revealed the non-uniform distribu-
tion of nanoparticles, which became ordered with smooth and
uniform background on annealing. EDX pattern confirmed
the formation of Cd0.5Zn0.5Se alloy and constituted with Cd,
Zn and Se. FTIR spectrum exhibits the presence of 2-ME as
capping agent and revealed that it is a good capping agent. Fi-
nally, UV–Visible absorption and PL spectra concluded that
the crystalline nature and the decreased optical band gap are
the significant properties for the fabrication of various opto-
electronic devices and other technological applications.
Acknowledgements
The authors gratefully acknowledge UGC-DAE IUC, Indore
(M.P.) for XRD, SEM, EDX, AFM and FTIR analysis,
Department of Chemistry, Govt. V.Y.T.P.G. Autonomous
College, Durg (C.G.) for optical absorption studies and Dr.
K.V.R. Murthy, M.S. University of Baroda, Vadodara for
S.R. Deo et al.
PL studies. One of the authors (SRD) expresses her gratitude
to the University Grants Commission (U.G.C.), New Delhi
for providing Maulana Azad National Fellowship (MANF).
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