Solid State Sciences 16 (2013) 102e110

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Solid State Sciences

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Review of CdO thin films

R. Chandiramouli a, B.G. Jeyaprakash a, b, *
a
School of Electrical & Electronics Engineering, SASTRA University, Tirumalaisamudram, Thanjavur 613 401, Tamilnadu, India
b
Centre for Nanotechnology & Advanced Biomaterials, SASTRA University, Tirumalaisamudram, Thanjavur 613 401, Tamilnadu, India

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

Article history: Cadmium Oxide (CdO) thin film is one of the first transparent conducting oxide semiconductors. Its
Received 29 December 2011 excellent optical and electronic properties have made CdO a promising material for flat panel displays. In
Received in revised form this article, we provide a comprehensive review of the state-of-the-art research activities related to the
21 June 2012
‘preparation-property-application’ triangle of CdO thin films.
Accepted 17 October 2012
Available online 25 October 2012
Ó 2012 Elsevier Masson SAS. All rights reserved.

Keywords:
Thin film
CdO
Vapour phase
Liquid phase
Band gap
Ternary
Nanostructured

1. Introduction the number of publications increases faster than in the first period.
After 2005, the rate of increase is more than doubled.
In recent years, cadmium oxide thin films have attracted
considerable attention due to the potential applications in opto-
electronics devices and chemical sensors. Although cadmium and 2. Preparation techniques of CdO thin films
its compounds are highly toxic, it is the key component in battery
production, colouring pigments, corrosion protection in steels, and Devices or components made in thin-film forms have advan-
barriers to control neutrons in nuclear fission. Historically, CdO was tages over those made from bulk materials because of superior
one of the first examples of a Transparent Conducting Oxide re- performance, extreme compactness and the corresponding reduc-
ported by Badeker in 1907 [1]. CdO crystallises into the NaCl tion in size and weight, low power consumption, etc. Thin films are
structure and does not undergo any phase transitions up to the deposited onto bulk materials (called the substrate) to achieve
highest pressure of w83 GPa [2]. Fig. 1 is a plot of the number of properties unattainable or not easily attainable by the substrate
articles related to binary, ternary and nanoparticle materials of CdO alone. A variety of thin-film materials, such as metals, semi-
with time. These data were obtained from the “Web of Science” conductors, insulators or dielectrics, are prepared by the various
database provided by Thomson Reuters. The total number of arti- preparative techniques that have been developed. Newer methods
cles is approximately 411, among which 266 papers were published are also being developed to improve the quality of the deposited
in the last 10 years. Three distinct periods are observed in this plot. material and the reproducibility of the properties. Any thin-film
The first period is up to the late 1990s, and no significant activities preparation techniques involve a) the production of the appro-
are observed. The second period of research is up to 2005, where priate atomic/molecular species, b) the transport of the species and
c) the condensation of the species onto the substrate. The tech-
niques of thin-film preparation can be classified as a) the vapour
phase and b) liquid phase techniques. Fig. 2 is a plot of CdO thin
films prepared by various techniques since 1975. The figure shows
* Corresponding author. Centre for Nanotechnology & Advanced Biomaterials,
SASTRA University, Tirumalaisamudram, Thanjavur 613 401, Tamilnadu, India.
that spray pyrolysis, one of the liquid phase techniques, was widely
Tel.: þ91 4362 264101x645, þ91 9865421411 (mobile); fax: þ 91 4362 264120. used, probably due to its simple doping process, cost-effectiveness
E-mail address: [email protected] (B.G. Jeyaprakash). and possibility of large area deposition. In the following section,

1293-2558/$ e see front matter Ó 2012 Elsevier Masson SAS. All rights reserved.
http://dx.doi.org/10.1016/j.solidstatesciences.2012.10.017
 R. Chandiramouli, B.G. Jeyaprakash / Solid State Sciences 16 (2013) 102e110 103

Fig. 1. Plot of number of articles related to binary, ternary and nanoparticle of CdO materials with time.

a brief summary is provided for CdO preparation by various tech- CdO film. The dopant levels were varied between 0.5 at% and
niques, and its properties are described. 10 at% to tune the electrical conductivity and the optical
transparency.
In the thermal evaporation technique, films grown either at
2.1. Vapour phase techniques
room temperature or at elevated temperature on an amorphous or
crystalline substrate were reported as polycrystalline and, in most
The vapour phase deposition technique involves the forma-
cases, with preferential orientation along (111) plane. Dakhel re-
tion of thin films by the condensation of a vaporised form of the
ported that Ce [7], Li [8], Dy [10], Sm [11] and Eu [12] doping in the
desired film material onto a substrate. A variety of methods for
CdO lattice broadens the impurity band and merge with the bottom
obtaining the vapour, such as thermal evaporation [3e12], pulsed
of the conduction band, causing a decrease in the effective band
laser deposition [13e24], sputtering [25e31], and metal organic
gap. For Fe doping levels greater than 3 wt%, the band gap increases
chemical vapour deposition [32e36], was employed to prepare
rather than decreases [9].
doped and undoped CdO thin films with thicknesses between
Sn [13,14], In [15,16], Ti [17e19], Al [22] and Gd [23] doped CdO
100 nm [17] and 632 nm [6]. The optical and electrical properties
films were deposited by pulsed laser deposition onto quartz
of semiconductors are easily modified by introducing the
substrates at different temperatures and oxygen partial pressures.
appropriate level of impurities (dopants) into their crystal
The peak-to-valley roughness of Ti doped CdO deposited onto
lattices. The dopants that produce the desired controlled changes
a quartz substrate at 150  C is 6.2e37.3 nm as the oxygen pressure
in the base materials are classified as p- or n-type. A survey of
varies from 1  104 to 1  101 mbar [19]. A lower peak-to-valley
literature shows that only n-type CdO films were deposited by
roughness is suitable to minimise the leakage current in photo-
vapour phase techniques using different elemental doping
voltaic applications. Ti [17], In [15] and Al [22] doped CdO films
methods and that no results are available for p-type CdO films.
prepared above 150  C were (200) oriented; otherwise, they have
This lack of p-type CdO is due to the native oxygen vacancy in the
both (111) and (200) orientations.
The grains orientation of CdO films deposited by DC reactive
sputtering depends on oxygen flow rate [27]. At low oxygen flow
rate, films were oriented along (200) plane and above 20 sccm were
along (111) plane. The mobility and carrier concentration decrease
with an increase in the oxygen flow rate. An average transmittance
of 85% in the visible region was obtained and depends on oxygen
flow rate.
Lamb and Irvine [33] prepared CdO films by metal organic
chemical vapour deposition using tertiary butanol as an oxygen
precursor and dimethyl cadmium as a cadmium source. CdO films
obtained at 280  C have a minimum resistivity of 3.9  104 U-cm
and an average transmittance of 80% in visible and IR region. This
near-IR transmittance, coupled with good electrical conduction, is
suitable to match the infrared requirements of multi-junction
photovoltaic devices that capture greater proportions of the solar
spectrum. Fig. 3 shows the variation of the energy band gap,
resistivity, carrier concentration and mobility of the doped CdO
Fig. 2. Plot of CdO thin films prepared by various techniques since 1975. films prepared by vapour phase techniques. The variation depends
104 R. Chandiramouli, B.G. Jeyaprakash / Solid State Sciences 16 (2013) 102e110

Fig. 3. Variation of the energy band gap, resistivity, carrier concentration and mobility of the doped CdO films prepared by vapour phase techniques.

on dopant level and preparation condition such as oxygen partial U-cm at room temperature, due to the removal of H2O vapour. The
pressure and annealing atmosphere. optical band gap decreases from 3.3 to 2.7 eV after annealing.
Singh et al. [47] prepared CdO nanostructured films of both (111)
2.2. Solution phase techniques and (200) preferential orientations by electro-deposition onto
indium-doped tin oxide conducting glass substrates at low
In these techniques, the unit species of the material to be temperatures (70, 80 and 90  C) from an aqueous solution using
deposited is dispersed in a liquid medium and is always present in CdCl2 as the Cd source. Henríquez et al. [49] synthesised template-
ionic form. This technique, therefore, inherently involves a chemical free CdO nanorods onto fluorine-doped tin oxide substrates using
and/or an electrochemical reaction for the formation of the film, CdCl2 at 150  C. The CdO nanorod film has (200) preferential
with the advantages of cost-effectiveness and large area deposition. orientation with a band gap of 2.52 eV.
Chemical bath deposition [37e43], SILAR [44e46], electrochemical Dakhel and Ali-Mohamed [54] reported the doping of Gd3þ with
deposition [47e52], solegel [53e65] and spray pyrolysis [66e95] a level of less than 2.4% enlarges the CdO unit cell slightly. The band
are solution phase techniques that were employed to prepare gap becomes wider for doping level larger than 2.4% compared to
undoped and doped CdO thin films with thicknesses between undoped CdO, the band gap suffers a narrowing of approximately
80 nm [45] and 1483 nm [71]. The survey shows that only n-type 13% due to a small doping level of (0.2%). The 2% Gd doped CdO film
CdO films were deposited by liquid phase techniques using different shows an increase of 320% conductivity, 92% increase in mobility and
doping elements, and no results are available for p-type CdO films. carrier concentration by 127% compared to undoped CdO film.
This is due to the native oxygen vacancy in the CdO film. The dopant Additionally, La-doped CdO thin films (1%, 5%, and 7%) have a slightly
levels were varied between 0.5 at% and 10 at% to tune the electrical higher lattice parameter and decrease the intrinsic energy gap from
conductivity and the optical transparency. 2.1 eV to 1.7 eV compared to undoped CdO [55]. The La-doped CdO
Salunkhe et al. [39] deposited Pd-sensitised CdO films by chem- films were degenerate semiconductors upto the atomic percentage
ical bath deposition from a precursor of Cd(NO3)2 complexed with of La dopant with 7%, beyond which the films were converted into
NH3 onto glass substrate. The dipping duration was 24 h. Pd sensi- a non-degenerate semiconductor. Ghosh et al. [58] reported that the
tisation was performed by dipping the CdO film for 5 s in a meth- excess of fluorine occupies the interstitial positions and in grain
anolic solution of PdCl2 and then drying it by air-flow. The film has boundaries of fluorine-doped CdO films prepared by solegel dip
both (111) and (200) preferential orientations with nano-fibrous method. The mobility of the undoped CdO films first increases
structure. Also, the same author reported CdO film deposition [44] with doping, reaching a maximum value and then decreases for
by immersing the glass substrate in cadmium nitrate solution of higher doping due to the variation of the grain boundary potential.
pH ¼ 12 as the Cd source and a 1% H2O2 solution, kept at 74  C. The An increase in the carrier concentration was achieved by
annealed films have both (111) and (200) preferential orientations. increasing the doping concentration, but this lowers the mobility
After annealing, electrical resistivity decreased from 102 to 103 due to enhanced charge carrier scattering from ionised impurities.
 R. Chandiramouli, B.G. Jeyaprakash / Solid State Sciences 16 (2013) 102e110 105

Akyuz et al. [67] reported that spray deposited fluorine-doped

CdO films have a slightly higher roughness compared to undoped
CdO. This rough film may be useful in single junction c-Si solar
cells. The interface between a high refractive index material (Si,
n w 3.7) and a low refractive index material (CdO:F, n w 1.6)
results in reduced reflection due to gradual refractive index
matching. This enables light trapping into the Si layer by scattering
at the interfaces, thereby increasing the optical path within the Si
layer.
Gurumurugan et al. [75] reported the variation in refractive
index from 1.68 to 2.84 in the wavelength range of 500e1500 nm of
CdO thin films with indirect and direct band gaps of 1.98 and
2.32 eV respectively. Laser damage studies at a wavelength of
1.06 mm shows that CdO thin films possess optical damage at the
threshold of approximately 2.37  104 J/m2. Vigil Galan et al. [88]
reported the enhancement of the preferential orientations along
(200) and (220) planes with the concentration of 1% Sn in the
solution. The maximum values of electrical conductivity and band
gap energy were achieved at this concentration.
Kumaravel et al. [91] reported a minimum resistivity of
3.4  104 U-cm with a carrier concentration of 4.12  1020/cm3 of
a spray deposited CdO film doped with 3 wt.% Al, and the band gap
value increases with doping, reaching a maximum of 2.53 eV when
the doping level is 3 wt.% and then decreases with higher Al-doping
concentrations. Irradiation of Ag9þ [92] decreases the surface
roughness of the CdO films from 39 to 29 nm. Khan et al. [84] also
reported the decrease in band gap caused by Al-doping in CdO
films. The conductivity of undoped CdO films shows metallic
behaviour at lower temperatures. This behaviour is absent with
doping of Al, and exhibits semiconducting behaviour for the entire
measured temperature range.
Kumaravel et al. [93] reported the increase in the packing
density of CdO films with the increase of indium doping concen-
tration and crystallites reorients along the (111) plane. A minimum
resistivity of 4.84  104 U-cm and a carrier concentration of
3.73  1020/cm3 with high transmittance in the range of 300e
1100 nm were achieved for 6 wt% indium doping. The band gap
of CdO increases upon increasing the doping concentration and
reaches a maximum value of 2.72 eV for 6 wt% indium doping from
2.36 eV of undoped film.
Crystalline nature and surface morphology of spray deposited Fig. 4. XRD pattern of spray deposited CdO film at different temperature (a) 200  C (b)
CdO film depends on the substrate temperature. Fig. 4 shows the 250  C and(c) 300  C.
XRD pattern of CdO film prepared onto glass substrate at different
temperatures. It shows that the crystallinity increases as substrate
temperature increases and also the (111) plane intensity increases. CdO usually exists in nonstoichiometric with pronounced cation
Fig. 5(aed) shows the surface morphology of the CdO film prepared interstitials or anion vacancies, resulting in a free electron
at different temperatures. As substrate temperature increases, well concentration of 1019e1021 cm3. Depending upon preparation or
defined grains can be seen. Fig. 6 shows the variation of the energy processing condition, it is either a non-degenerate or degenerate n-
band gap, resistivity, carrier concentration and mobility of the type semiconductor. The ionised donors gives rise to an impurity
doped CdO film prepared from a liquid phase technique. The vari- level below to the conduction band and depending upon carrier
ation depends on dopant level. Table 1 shows a comparison of concentration, the impurity band may overlap with the conduction
energy band gap, resistivity, carrier concentration and mobility of band in CdO and giving rise to quasi-metallic or metallic properties.
Sn- and Al-doped CdO film by vapour and liquid phase techniques. Electrical resistivity and mobility strongly depends on dopant size,
It shows the preparation technique also change the properties for preparation condition and temperature. When the ionic radii of
same dopant in CdO film. dopant is similar to ionic radius of Cd2þ, the mobility and
conductivity are independent of temperature below 100 K, due to
2.3. Discussion on various properties ionised and neutral impurities scattering process. At high temper-
ature beyond 100 K, the conductivity and mobility decreases with
Based on preparation and processing condition, in general at increase in temperature due to lattice vibration scattering which
ambient pressure, CdO crystallises in the cubic rock-salt (NaCl) further depends on temperature.
structure with lattice constant of 4.694  A. However first-principle The crystal colour varies from brown to orangeeyellow which
calculation shows a phase transition from NaCl to CsCl structure depends on the cadmium atom concentration. The colour also
at a pressure of 83.1 GPa [2]. Dopant of smaller ionic radii compared varies with respect to particle size. The direct optical band gap of
with Cd2þ makes relaxation of oxide anions around cation dopant bulk CdO is 2.20 eV which has a relatively low optical transparency
and inturn gives weaker CdeO hybridisation [96]. in the visible region. However doping of aliovalent metals like Y, Sc,
106 R. Chandiramouli, B.G. Jeyaprakash / Solid State Sciences 16 (2013) 102e110

Fig. 5. Scanning electron micrograph of spray deposited CdO film at different temperature (a) 200  C (b) 220  C (c) 240  C and (d) 260  C from 0.05 M of precursor solution
concentration.

In, etc, offers the flexibility of tuning the band gap with a carrier ionic radii of dopant is comparable or larger than with Cd2þ will
density dependent Moss-Burstein shift [96]. Smaller ionic radii of leads to band gap widening. Due to these reasons, CdO-based
dopant compared with ionic radii of Cd2þ result in band gap nar- materials which have simple cubic rock-salt structure leads as
rowing due to shrinkage of lattice parameters, in contrast when the TCOs material.

Fig. 6. Variation of the energy band gap, resistivity, carrier concentration and mobility of the doped CdO films prepared by liquid phase techniques.
 R. Chandiramouli, B.G. Jeyaprakash / Solid State Sciences 16 (2013) 102e110 107

Table 1
Comparison of energy band gap, resistivity, carrier concentration and mobility of the Sn- and Al-doped CdO films prepared by vapour and liquid phase techniques.

Dopant Preparation Band gap (eV) Resistivity (103 U-cm) Carrier concentration (1020cm3) Mobility (cm2/Vs) Reference
method
Min. Max. Min. Max. Min. Max. Min. Max.
Sn PLD 2.93 e 0.025 0.22 5.0 55.0 40 75 [14]
SP 2.52 2.91 0.42 0.63 5.0 7.0 13 25 [88]
PLD e e 0.01 0.275 10 20 10 150 [16]
SP 2.45 2.72 0.5 0.875 1.6 3.6 30 65 [93]
Al SPT 2.43 2.53 2.70 4.0 0.034 1.06 194.57 459.56 [26]
SG e e 0.6 1.25 0.43 1.07 35 250 [61]
SP 2.34 2.48 e e 9.3 17.3 22.3 30.94 [84]

PLD e Pulsed Laser Deposition, SP e Spray pyrolysis, SPT e Sputtering, SG e SoleGel.

Thermal and elastic properties can be invoked through Debye was obtained from the 25 h deposition. This low contact angle
temperature and for CdO, the Debye temperature depends on indicates that the surface of the film is hydrophilic in nature, which
pressure and temperature. From First-principle calculation, it is an essential factor for gas sensing application [103].
shows 336.5 K at zero pressure and 0 K. Initially, the Debye Bazargan et al. [104] prepared CdO nanofibres of 50e60 nm
temperature increases with increase in pressure upto 80 GPa and diameters by the electro-spinning method onto silicon substrates,
then it decreases beyond 80 GPa due phase transition [2]. which is calcined at 450  C for 30 min. A 72% weight loss of
precursor fibres was seen during calcination. The room-
3. Ternary compounds temperature photoluminescence spectrum has two emission
peaks at 493 and 528 nm. The first peak is attributed to the exci-
Ternary oxides Mx1My2Oz, (where M1 and M2 are metals) of CdO tonic transitions, which are size-dependent, and the second one
[31,57,97e102] have recently attracted attention because of their can be ascribed to the deep-trap emission and surface-state emis-
high carrier mobility, stability and good optical transparency. sion, which are less size-dependent.
CdZnO, Cd2SnO4 and CdIn2O4 thin films were prepared to have
enhanced properties over binary CdO films. 5. Applications
Li et al. [97] observed near-band-edge photoluminescence
emission (from 2.39 to 2.74 eV) of CdZnO films grown by plasma- 5.1. Electrochemical capacitor
assisted molecular-beam epitaxy on c-plane sapphire substrate.
Pure wurtzite CdZnO shows an insignificant photoluminescence Chang et al. [50] reported the mechanism of charge storage in
peak shift, but after rapid thermal annealing, the wurtzite and rock- a CdO electrode based on the principle of the intercalation and de-
salt structural mixture of CdZnO exhibits blue shifts due to the intercalation of cations in the oxidation and reduction phenom-
phase change. enon. The redox reactions given below depend upon the presence
Kumaravel and Ramamurthi [100] reported highly conducting of cations in the electrolyte, and in aqueous solution, the contri-
and transparent indium-doped Cd2SnO4 films deposited onto bution of cations to the pseudo-capacitance process is quite
Corning substrates at 525  C. A minimum resistivity of significant.
1.76  0.2  103 U-cm and a maximum carrier concentration of
9.812  0.4  1019/cm3 occur for 1 wt.% In-doped film. Doping of In CdOþdHðor any cationsÞþ þde /de CdO1d
in Cd2SnO4 films widens the band gap from 2.98  0.1 to ðOHðor any cationsÞÞd
3.04  0.1 eV. Flores Mendoza et al. [57] observed the formation of
a CdIn2O4 phase when the indium content in the precursor The specific capacitance (SC) of a CdO electrode in 1 M KOH is
cadmium acetate solution is 10 at% and when the sintering 343 mF/g and is higher than those in KNO3 (125 mF/g), Na2SO4
temperature is 450  C. (302 mF/g) and NaOH (337 mF/g) in the potential window ranging
from 0.4 to 0.4 V. The cyclic voltammetry curves of the CdO
4. Nanostructured films electrodes, annealed above 200  C and 400  C temperature,
demonstrate excellent reversibility and reveal the essential nature
One-dimensional nanostructured thin films have received of the CdO matrix instead of Cd(OH)2 for electrochemical capacitor
significant attention due to their potential applications in nano- applications. A decrease in the SC value is reported with an increase
scaled electronic and optoelectronic devices. These structures in the scan rate due to the presence of inner active sites, which
with high aspect ratios offer a higher integration density, lower cannot precede the redox transitions completely. The maximum
power consumption, tuning of the band gap and enhanced sensing and minimum values of SC found to be 350 and 220 mF/g which
performance. was obtained at 10 and 200 mV/s respectively. The CdO film elec-
Dhawale et al. [40] prepared CdO nanowires by the chemical trode can withstand over 1000 cycles without any drastic decrease
bath deposition method onto glass substrates. The wires were in the SC value which infers that the CdO electrode material is the
randomly distributed with 60e65 nm diameters and lengths of suitable as supercapacitors for energy storage.
2.5e3 microns. The direct and indirect band gap of the CdO Abrutis et al. [99] reported the capacitive property of poly-
nanowires was found to be 2.42 and 2.40 eV, respectively, and are crystalline Cd2SnO4 (CTO) film. The semi-circular radius of the
slightly higher than bulk CdO. Kamble et al. [37] synthesised CdO electrochemical impedance spectra shows a decrease with higher
nanowires onto glass substrates by the chemical bath deposition bias potential. The MotteSchottky plots indicate the linear
method with 90e100 nm diameters, and as the deposition time dependence of the differential electrode capacitance vs. potential
increased from 25 to 100 h, the nanowires converted into nano- up to þ0.4 V, and the slope is inversely proportional to the charge
cubes. The lowest contact angle of 18 was observed for the film carrier concentration, was reported as 6.72  108 F1 V1 cm2.
obtained from the 100 h deposition, and the highest angle of 45 The flat band potential was found to be 0.2 V and was higher than
108 R. Chandiramouli, B.G. Jeyaprakash / Solid State Sciences 16 (2013) 102e110

solegel derived CTO films. The electrochemical activity of the

Cd2SnO4 films was tested using two redox systems: hexacyano
ferro/ferricyanide (FC), and safranine T (ST). The midpoint
potentials for FC and ST redox systems were found to be 0.230 V
and 0.495 V respectively and were found to be considerably
higher on the spray deposited CTO electrodes.

5.2. Nonlinear optics

Henari and Dakhel [105] reported the nonlinear optical prop-

erties of CdO thin films deposited on Si and glass substrates by the
slow evaporation method. The films are post-annealed at 300  C in
a pure hydrogen atmosphere for 30 min. The nonlinear mecha-
nisms of refractive index (n) and absorption (a) are related to the
incident laser intensity I, as

n ¼ n0 þ n2 I
Fig. 7. Variation of spray deposited CdO film resistance under air and 500 ppm of
and ethanol atmosphere at different operating temperature.

a ¼ a0 þ bI
increased, and was found to be a maximum for a 1.5 mm thick CdO
where no and ao are the linear refractive index and the linear film. A small response (20 s) and recovery time (30 s) was reported
absorption coefficient, n2 is the nonlinear refractive index and b is for CdO with a 0.43 mm film thickness. Also, the nano-fibrous CdO
the nonlinear absorption coefficient. The normalised transmittance structure deposited by the chemical bath method [41] shows
without the aperture as a function of distance along the lens Z-axis a maximum response at an operating temperature of 425  C, with
for the CdO film is symmetric and demonstrates optical limiting. response and recovery times of 70 s and 80 s, respectively. CdO
The open z-scan performed at different intensities, ranging from films prepared by the spray pyrolysis method [80] were reported to
1.6  107 to 5.1  105 W/m2, reported no intensity dependent respond more selectively for LPG over N2 compared to CO2 at an
behaviour and indicates a third-order nonlinear optical effect. The operating temperature of 425  C. The response increased from 15 to
nonlinear absorption coefficient was approximately 1.7  102 m/ 34.11% as the LPG concentration increased from 0.06 to 0.16 vol.%.
W and is three orders of magnitude higher than a zinc porphyrin The response improved by up to 35% at an optimum operating
polymer. This high nonlinear absorption coefficient is due to the temperature of 275  C after Pd sensitisation [39]. The Pd-sensitised
increase in the electron density in the conduction band as a result CdO film showed more selectivity towards LPG compared to CO2.
of the hydrogenation. The value of the nonlinear refractive index Kamble et al. [43] reported ethanol sensing by nanowire and
was reported to be 6.1  108 m2/W at 633 nm. This nonlinear nanowall structured CdO films prepared by chemical bath deposi-
refractive index is smaller by one order of magnitude than the value tion. At low temperatures, the sensor response is limited by the rate
observed for pure CdO at 514 nm measured in CW mode. The of chemical reaction, and at higher temperatures, the sensor
excited state absorption cross-section is 8.85  1019 m2 and was response is limited by the rate of diffusion of gas molecules. The
higher than the ground state, indicating that the nonlinearity is maximum 15.3% response is obtained for the nanowire CdO films
associated with the optical limiting activity. within 48 s, while a 23% response is obtained for nanowalls within
19 s at 400  C. The enhanced sensitivity is due to the high porosity
5.3. Photoluminescence and hydrophilic nature of the nanowall structured CdO film.

Moholkar et al. [86] reported the observation of room-

temperature photoluminescence (PL) green emission peaks at
482 nm from Ga-doped CdO films and the relative intensity
depends on the deposition temperature. Oxygen vacancies are the
dominant luminescent centres for the green emission. Deokate
et al. [85] also reported room-temperature PL emission spectra
from pure and Ga-doped CdO thin films excited at 325 nm. The
green PL emission intensity (around 470 nm) increases with an
increasing [Ga]/[Cd] ratio in the deposited CdO thin films. The green
emission is due to the presence of various point defects and also the
concentration of free electrons.

5.4. Gas sensing

Salunkhe and Lokhande [44] reported the LPG sensing property

of SILAR-deposited CdO thin film. The CdO-based sensor shows the
maximum response at an operating temperature of 425  C. At
425  C, the response increased from 7.89 to 14.2% as the LPG
concentration increased from 0.04 to 0.1 vol%. At concentrations
above 0.08%, the response value was gradual and saturated. The Fig. 8. Plot of CdO film response vs. operating temperature for different ethanol
sensor sensitivity was found to increase as the film thickness concentration.
 R. Chandiramouli, B.G. Jeyaprakash / Solid State Sciences 16 (2013) 102e110 109

be on the order of 103 V/K for both as-deposited and annealed

films, and Gurumurugan et al. [75] reported a value on the order of
106 V/K. Ismail [77] reported that the Seebeck coefficient of CdO
film is negative, indicating n-type conductivity. The origin of the n-
type nature is native defects, such as oxygen vacancies and
cadmium interstitials. The Seebeck coefficient is increased with
increasing temperature of the films due to the increase in electron
concentration. The activation energy was found to vary from 0.32 to
0.9 eV depending on the annealing time. Khan et al. [84] reported
that the thermo-electric power varies from 0.01 to 0.04 mV/K as the
Al-doping varies from 0 to 2% in CdO films.

6. Conclusion and future outlook

This review has summarised the techniques used to deposit

cadmium oxide thin films on different substrates, with a particular
emphasis on the most chemically stable form, CdO. All the prepa-
Fig. 9. Dynamic response of CdO film at 250  C for 500 ppm of ethanol.
ration techniques have contributed to the wide range of applica-
tions. Depending on the deposition conditions and preparation
Fig. 7 shows the spray deposited CdO film resistance in air and methods, CdO films can have considerably different microstruc-
ethanol atmosphere. The temperature at which the resistance is tural, optical, and electrical properties. We have used reported band
minimum in ethanol atmosphere is the actual thermal energy gaps, resistivity, thermo-emf, and preferential growth planes to
needed to activate the material for sensing and is around 250  C for compare films deposited from different techniques. Regarding the
500 ppm of ethanol. Fig. 8 shows that the response is maximum at outlook for CdO thin films, we believe that future applications and
250  C for 100e1000 ppm level of ethanol. Also the increasing rate research will be focused primarily on the magnetic and gas sensing
of response for various ethanol concentrations was comparatively properties. CdO in bulk form is diamagnetic in nature, and recently,
larger up to 800 ppm and then almost saturated. This is because, Al-doped CdO film deposited at 25  C and 100  C onto p-type
the ethanol molecules cover the entire surface of the film and hence silicon substrate exhibited paramagnetic behaviour, while the films
the excess ethanol molecules would not react on the surface of CdO deposited at temperatures ranging from 200 to 400  C exhibited
film. This limit the response at higher concentration and thus, the a ferromagnetic nature due to the predominant (200) orientation.
active region of CdO film would be up to 800 ppm of ethanol. Fig. 9 Cadmium-based ternary oxide has also been recently prepared
shows the dynamic response of CdO film in air and ethanol atmo- [106] for transparent thin-film transistors. Different nano-
sphere. The response and recovery time was found to be 40 and 75 s structured forms of CdO films exhibited enhanced performance in
respectively. sensing applications [43,44,80]. Thus, the potential use of such CdO
nanostructured materials provides excellent possibilities for
designing devices.
5.5. Solar cells

Yakuphanoglu et al. [64] reported the performance of solegel References

spin coated n-CdO/p-Si heterojunction diode. The diode exhibited
a rectifying ratio of 37 at 2 V with an ideality-factor of 5.41 and [1] K. Badeker, Ann. Phys. (Leipzig) 22 (1907) 749.
[2] Feng Peng, Qiang Liu, Hongzhi Fu, Xiangdong Yang, Solid State Commun. 148
having series resistance of 6.41 kU. The diode has a maximum open (2008) 6e9.
circuit voltage of 0.12 V and short-circuit current of 0.53  106 A. [3] C. Dantus, G.G. Rusu, M. Dobromir, M. Rusu, Appl. Surf. Sci. 255 (2008) 2665.
The interface state density value varies from 7.82  1013 to [4] H.B. Lu, L. Liao, H. Li, Y. Tian, D.F. Wang, J.C. Li, Q. Fu, B.P. Zhu, Y. Wu, H.B. Lu,
L. Liao, H. Li, Y. Tian, D.F. Wang, J.C. Li, Q. Fu, B.P. Zhu, Y. Wu, Mater. Lett. 62
3.02  1012 eV1cm2 under various bias voltages. Nanoclusters of (2008) 3928.
CdO deposited onto a p-Si substrate are reported to have an open [5] A.A. Dakhel, J. Mater. Sci. 46 (2011) 1455.
circuit voltage of 0.41 V and a short-circuit current density of [6] A.A. Dakhel, F.Z. Henari, Cryst. Res. Technol. 38 (2003) 979.
[7] A.A. Dakhel, Mater. Chem. Phys. 130 (2011) 398.
2.19 mA/cm2 under AM1.5 illumination. These values are lower [8] A.A. Dakhel, Solid State Sci. 13 (2011) 1000.
than other solar cells, and this study opens the possibilities for [9] A.A. Dakhel, Thin Solid Films 518 (2010) 1712.
further development. [10] A.A. Dakhel, Sol. Energy 83 (2009) 934.
[11] A.A. Dakhel, Mater. Chem. Phys. 117 (2009) 284.
Murali et al. [61] reported solar cell studies of solegel dip-coated
[12] A.A. Dakhel, Opt. Mater. 31 (2009) 691.
Al-doped CdO onto p-Si substrates. The electrical conductivity of an [13] B.J. Zheng, J.S. Lian, L. Zhao, Q. Jiang, Vacuum 85 (2011) 861.
undoped film was 0.5  103 mho cm1 and increased to [14] R.K. Gupta, K. Ghosh, R. Patel, S.R. Mishra, P.K. Kahol, Mater. Lett. 62 (2008)
1.5  103 mho cm1 after doping. The mobility decreased from 250 4103.
[15] B.J. Zheng, J.S. Lian, L. Zhao, Q. Jiang, Appl. Surf. Sci. 256 (2010) 2910.
to 35 cm2 V1s1 with an increase of the Al concentration. Solar cell [16] R.K. Gupta, K. Ghosh, R. Patel, S.R. Mishra, P.K. Kahol, Mater. Lett. 62 (2008)
studies performed under an illumination of 90 mW/cm2 have an 3373.
open circuit voltage of 0.62 V, short-circuit current density of [17] R.K. Gupta, K. Ghosh, R. Patel, P.K. Kahol, Appl. Surf. Sci. 255 (2009) 6252.
[18] B. Saha, R. Thapa, K.K. Chattopadhyay, Solid State Commun. 145 (2008) 33.
16 mA/cm2 and 9.55% efficiency. [19] R.K. Gupta, K. Ghosh, R. Patel, P.K. Kahol, Appl. Surf. Sci. 255 (2008) 2414.
[20] M. Yan, M. Lane, C.R. Kannewurf, R.P.H. Chang, Appl. Surf. Sci. 78 (2001)
2342.
5.6. Thermo-emf
[21] Raid A. Ismail, Bassam G. Rasheed, Evan T. Salm, Mukram Al-Hadethy,
J. Mater. Sci. Mater. Electron. 18 (2007) 1027.
Salunkhe et al. [46] reported the observation of thermo-emf in [22] K. Siraj, M. Khaleeq-ur-Rahman, S.I. Hussain, M.S. Rafique, S. Anjum, J. Alloy
the temperature range of 27e127  C from SILAR-deposited CdO Compd. 509 (2011) 6756.
[23] R.K. Gupta, K. Ghosh, R. Patel, P.K. Kahol, J. Alloy Compd. 509 (2011) 4146.
films. The hot end shows positive polarity, which confirmed the n- [24] R.K. Gupta, K. Ghosh, R. Patel, P.K. Kahol, Phys. E 44 (2011) 163.
type nature of the film. The thermo-electric power was reported to [25] B. Saha, R. Thapa, N.S. Das, K.K. Chattopadhyay, Indian J. Phys. 84 (2010) 681.
110 R. Chandiramouli, B.G. Jeyaprakash / Solid State Sciences 16 (2013) 102e110

[26] B. Saha, S. Das, K.K. Chattopadhyay, Sol. Energ. Mater. Sol. Cell 91 (2007) [68] R. Ferro, J.A. Rodríguez, Thin Solid Films 347 (1999) 295.
1692. [69] R.J. Deokate, S.M. Pawar, A.V. Moholkar, V.S. Sawant, C.A. Pawar, C.H. Bhosale,
[27] Qiang Zhou, Zhenguo Ji, BinBin Hu, Chen Chen, Lina Zhao, Chao Wang, Mater. K.Y. Rajpure, Appl. Surf. Sci. 254 (2008) 2187.
Lett. 61 (2007) 531. [70] Metin Kul, Muhsin Zor, Ahmet Senol Aybek, Sinan Irmak, Evren Turan, Sol.
[28] B. Saha, R. Thapa, K.K. Chattopadhyay, Sol. Energ. Mater. Sol. Cell 92 (2008) Energ. Mater. Sol. Cell 91 (2007) 882.
1077. [71] Metin Kul, Muhsin Zor, Ahmet Senol Aybek, Sinan Irmak, Evren Turan, Sol.
[29] Ueda Naoyuki, Maeda Hiroo, Hosono Hideo, Kawazoe Hiroshi, J. Appl. Phys. Energ. Mater. Sol. Cell 91 (2007) 1927.
84 (1998) 6174. [72] Metin Kul, Muhsin Zor, Ahmet Senol Aybek, Sinan Irmak, Evren Turan, Thin
[30] T.K. Subramanyam, B. Radhakrishnan, S. Uthanna, B. Srinivasulu Naidu, Solid Films 515 (2007) 8590.
P. Jayarama Reddy, J. Mater. Sci. Lett. 16 (1997) 1576. [73] K. Gurumurugan, D. Mangalaraj, Sa.K. Narayandass, J. Cryst. Growth 147
[31] Ruijie Zhang, Peiliang Chen, Yuanyuan Zhang, Xiangyang Ma, Deren Yang, (1995) 355.
J. Cryst. Growth 312 (2010) 1908. [74] K. Gurumurugana, D. Mangalaraj, Sa.K. Narayandass, Thin Solid Films 251
[32] D.A. Lamb, S.J.C. Irvine, J. Cryst. Growth 332 (2011) 17. (1994) 7.
[33] D. Lamb, S.J.C. Irvine, Thin Solid Films 518 (2009) 1222. [75] K. Gurumurugan, D. Mangalaraj, S.K. Narayandass, K. Sekar, C.P. Girija Val-
[34] D.M. Ellis, S.J.C. Irvine, J. Mater. Sci. Mater. Electron. 15 (2004) 369. labhan, Semicond. Sci. Technol. 9 (1994) 1827.
[35] Wang Lian, Yang Yu, Jin Shu, Marks Tobin, J. Appl. Phys. Lett. 88 (2006) [76] K. Gurumurugan, D. Mangalaraj, Sa.K. Narayandass, Y. Nakanishi, Y. Hatanaka,
162115. Appl. Surf. Sci. 113 (1997) 422.
[36] S.K. Vasheghani Farahani, T.D. Veal, P.D.C. King, J. Zuniga-Perez, V. Munoz- [77] Raid A. Ismail, J. Mater. Sci. Mater. Electron. 20 (2009) 1219.
Sanjose, C.F. McConville, J. Appl. Phys. 109 (2011) 073712. [78] L.C.S. Murthy, K.S.R.K. Rao, Bull. Mater. Sci. 22 (1999) 953.
[37] A.S. Kamble, R.C. Pawar, J.Y. Patil, S.S. Suryavanshi, P.S. Patil, J. Alloy Compd. [79] M.D. Uplane, P.N. Kshirsagar, B.J. Lokhande, C.H. Bhosale, Mater. Chem. Phys.
509 (2011) 1035. 64 (2000) 75.
[38] Hani Khallaf, Chia-Ta Chen, Liann-Be Chang, Oleg Lupan, Aniruddha Dutta, [80] R.R. Salunkhe, D.S. Dhawale, D.P. Dubal, C.D. Lokhande, Sensor Actuator B
Helge Heinrich, A. Shenouda, Lee Chow, Appl. Surf. Sci. 257 (2011) 9237. 140 (2009) 86.
[39] R.R. Salunkhe, D.S. Dhawale, U.M. Patil, C.D. Lokhande, Sensor Actuator B 136 [81] B.J. Lokhande, M.D. Uplane, Mater. Res. Bull. 36 (2001) 439.
(2009) 39. [82] C.H. Bhosale, A.V. Kambale, A.V. Kokate, K.Y. Rajpure, Mater. Sci. Eng. B 122
[40] D.S. Dhawale, A.M. More, S.S. Latthe, K.Y. Rajpure, C.D. Lokhande, Appl. Surf. (2005) 67.
Sci. 254 (2008) 3269. [83] B.J. Lokhande, P.S. Patil, M.D. Uplane, Mater. Chem. Phys. 84 (2004) 238.
[41] R.R. Salunkhe, V.R. Shinde, C.D. Lokhande, Sensor Actuator B 133 (2008) 296. [84] M.K.R. Khan, M. Azizar Rahman, M. Shahjahan, M. Mozibur Rahman,
[42] K.L. Narayanan, K.P. Vijayakumar, K.G.M. Nair, G.V.N. Rao, Bull. Mater. Sci. 20 M.A. Hakim, Dilip Kumar Saha, Jasim Uddin Khan, Curr. Appl. Phys. 10
(1997) 287. (2010) 790.
[43] A.S. Kamble, R.C. Pawar, N.L. Tarwal, L.D. More, P.S. Patil, Mater. Lett. 65 [85] R.J. Deokate, S.V. Salunkhe, G.L. Agawane, B.S. Pawar, S.M. Pawar,
(2011) 1488. K.Y. Rajpurea, A.V. Moholkar, J.H. Kim, J. Alloy Compd. 496 (2010) 357.
[44] R.R. Salunkhe, C.D. Lokhande, Sensor Actuator B 129 (2008) 345. [86] A.V. Moholkar, G.L. Agawane, Kyu-Ung Sim, Ye-bin Kwon, Doo Sun Choi,
[45] M. Ali Yıldırım, Aytunc Ates, Sensor Actuator A 155 (2009) 272. K.Y. Rajpured, J.H. Kima, J. Alloy Compd. 506 (2010) 794.
[46] R.R. Salunkhe, D.S. Dhawale, T.P. Gujar, C.D. Lokhande, Mater. Res. Bull. 44 [87] F. Atay, I. Akyuz, S. Kose, E. Ketenci, V. Bilgin, J. Mater. Sci. Mater. Electron. 22
(2009) 364. (2011) 492.
[47] Trilok Singh, D.K. Pandya, R. Singh, Mater. Sci. Eng. B 176 (2011) 945. [88] O. Vigil Galan, Y. Sanchez Gonzalez, A. Arias Carbajal, G. Contreras Puente,
[48] Jinho Chang, Rajaram S. Mane, Dukho Ham, Wonjoo Lee, Byng Won Cho, M. Tufino Velazquez, C.M. Ruiz, Phys. Status Solidia A 203 (2006) 3713.
Joong Ki Lee, Sung-Hwan Han, Electrochim. Acta 53 (2007) 695. [89] R. Ferro, J.A. Rodriguez, O. Vigil, A. Morales-Acevedo, G. Contreras-Puente,
[49] R. Henríquez, P. Grez, E. Muñoz, H. Gómez, J.A. Badán, R.E. Marotti, Phys. Status Solidia A 177 (2000) 477.
E.A. Dalchiele, Thin Solid Films 518 (2010) 1774. [90] O. Vigil, F. Cruz, A. Morales-Acevedo, G. Contreras-Puentea, L. Vaillant,
[50] Jinho Chang, V.V. Todkar, Rajaram S. Mane, Dukho Ham, T. Ganesh, Sung- G. Santana, Mater. Chem. Phys. 68 (2001) 249.
Hwan Han, Phys. E 41 (2009) 1741. [91] R. Kumaravel, S. Menaka, S. Regina Mary Snega, K. Ramamurthi,
[51] R. Henríquez, P. Grez, E. Muñoz, E.A. Dalchiele, R.E. Marotti, H. Gómez, Thin K. Jeganathan, Mater. Chem. Phys. 122 (2010) 444.
Solid Films 520 (2011) 41. [92] R. Kumaravel, K. Ramamurthi, Indra Sulania, K. Asokan, D. Kanjilal,
[52] X.S. Peng, X.F. Wang, Y.W. Wang, C.Z. Wang, G.W. Meng, L.D. Zhang, J. Phys. D D.K. Avasti, P.K. Kulria, Radiat. Phys. Chem. 80 (2011) 435.
Appl. Phys. 35 (2002) 101. [93] R. Kumaravel, K. Ramamurthi, V. Krishnakumar, J. Phys. Chem. Solids 71
[53] A. Abdolahzadeh Ziabari, F.E. Ghodsi, J. Alloy Compd. 509 (2011) 8748. (2010) 1545.
[54] A.A. Dakhel, A.Y. Ali-Mohamed, J. Sol-Gel Sci. Technol. 55 (2010) 348. [94] C. Sravani, P. Sreedhara Reddy, P. Jayarama Reddy, Mater. Lett. 12 (1992) 406.
[55] A.A. Dakhel, A.Y. Ali-Mohamed, J. Sol-Gel Sci. Technol. 44 (2007) 241. [95] B.G. Jeyaprakash, K. Kesavan, R. Ashok Kumar, S. Mohan, A. Amala Rani, Bull.
[56] M.A. Flores, R. Castanedo, G. Torres, O. Zelaya, Sol. Energ. Mater. Sol. Cell 93 Mater. Sci. 34 (2011) 601.
(2009) 28. [96] Yu Yang, Shu Jin, Julia E. Medvedeva, John R. Ireland, Andrew W. Metz,
[57] M.A. Flores Mendoza, R. Castanedo Pérez, G. Torres Delgado, O. Zelaya Angel, Jun Ni, Mark C. Hersam, Arthur J. Freeman, Tobin J. Marks, J. Am. Chem. Soc.
Thin Solid Films 518 (2009) 1114. 127 (2005) 8796e8804.
[58] P.K. Ghosh, S. Das, S. Kundoo, K.K. Chattopadhyay, J. Sol-Gel Sci. Technol. 34 [97] L. Li, Z. Yang, Z. Zuo, J.H. Lim, J.L. Liu, Appl. Surf. Sci. 256 (2010) 4734.
(2005) 173. [98] Waleed E. Mahmoud, A.A. Al-Ghamdi, Opt. Laser Technol. 42 (2010) 1134.
[59] P.K. Ghosh, S. Das, K.K. Chattopadhyay, J. Nanopart. Res. 7 (2005) 219. [99] A. Abrutis, G. Valincius, G. Baltrunas, L. Parafionovic, A. Valiuniene, Z. Saltyte,
[60] R.K. Gupta, F. Yakuphanoglu, F.M. Amanullah, Phys. E 43 (2011) 1666. Thin Solid Films 515 (2007) 6817.
[61] K.R. Murali, A. Kalaivanan, S. Perumal, N. Neelakanda Pillai, J. Alloy Compd. [100] R. Kumaravel, K. Ramamurthi, J. Alloy Compd. 509 (2011) 4390.
503 (2010) 350. [101] Yasemin Caglar, Mujdat Caglar, Saliha Ilican, Aytunc Ates, J. Phys. D Appl.
[62] M.A. Flores Mendoza, R. Castanedo Pérez, G. Torres Delgado, O. Zelaya Angel, Phys. 42 (2009) 065421.
Sol. Energ. Mater. Sol. Cell 94 (2010) 80. [102] Ma De-Wei, Ye Zhi-Zhen, Huang Jing-Yun, Zhao Bing-Hui, Wan Shou-Ke,
[63] M. Caglar, F. Yakuphanoglu, J. Phys. D Appl. Phys. 42 (2009) 045102. Sun Xue-Hao, Wang Zhan-Guo, Chin. Phys. Lett. 20 (2003) 942.
[64] Fahrettin Yakuphanoglu, Mujdat Caglar, Yasemin Caglar, Saliha Ilican, J. Alloy [103] X. Xu, J. Wang, Y. Long, Sensors 6 (2006) 1751.
Compd. 506 (2010) 188. [104] A.M. Bazargan, S.M.A. Fateminia, M. Esmaeilpour Ganji, M.A. Bahrevar, Chem.
[65] Fahrettin Yakuphanoglu, Appl. Surf. Sci. 257 (2010) 1413. Eng. J. 155 (2009) 523.
[66] V. Bilgin, I. Akyuz, S. Kose, F. Atay, Semicond. Sci. Technol. 21 (2006) 579. [105] F.Z. Henari, A.A. Dakhel, Laser Phys. 18 (2008) 1557.
[67] I. Akyuz, S. Kose, E. Ketenci, V. Bilgin, F. Atay, J. Alloy Compd. 509 (2011) 1947. [106] Deuk-Hee Lee, Sangsig Kim, Sang Yeol Lee, Thin Solid Films 519 (2011) 4361.