Short review on chemical bath deposition of thin film and characterization

, ,
Dhananjay Mugle and Ghanshyam Jadhav

Citation: 1728, 020597 (2016); doi: 10.1063/1.4946648

View online: http://dx.doi.org/10.1063/1.4946648
View Table of Contents: http://aip.scitation.org/toc/apc/1728/1
Published by the American Institute of Physics
Short Review on Chemical Bath Deposition of Thin film and
Characterization
Dhananjay Mugle1,a) and Ghanshyam Jadhav 1, b)
1
Depertment of Physics, Shri Chhatrapati Shivaji College, Omerga-413606, India.
a)
dhananjayforu@gmail.com
b)
ghjadhav@rediffmail.com

Abstract. This reviews the theory of early growth of the thin film using chemical deposition methods. In particular, it
critically reviews the chemical bath deposition (CBD) method for preparation of thin films. The different techniques used
for characterizations of the chemically films such as X-ray diffractometer (XRD), Scanning electron microscopy (SEM),
Transmission electron microscopy (TEM), Electrical conductivity and Energy Dispersive Spectroscopy (EDS) are
discussed. Survey shows the physical and chemical properties solely depend upon the time of deposition, temperature of
deposition.

INTRODUCTION
This Global warming, environmental pollution, and impending shortage of fossil fuel sources are factors that
force modern society towards an increase in the utilization of renewable sources of energy. One of the most
abundant resources on the surface of the earth is sunlight. Sunlight reaches the earth in a quantity that is sufficient to
supply the total global energy consumption [1]. The use of solar energy has many advantages such as [2], it is free
and abundant. it has low environmental impact. It does not require large centralized supplies or expensive
distribution networks. Solar energy has high public acceptance as a natural form of energy.
The conversion of solar energy into usable form like solar cell devices play vital role in converting solar energy
into usable form. In this Technique generally use of thin films to convert solar energy to usable form. There are lots
of thin films which are made by the researchers. There are many techniques available for researchers in the
deposition of thin film of Different material on the layer [3], Like evaporation, sputtering, and chemical bath
deposition(CBD), sol gel[3]. The chemical bath deposition (CBD) method is grater commercial value than either
thermal evaporation or sputtering [4].
In the past few years, II-IV semiconductors thin films have attracted considerable attention from the research
community because of their wide range of applications in the fabrication of solar cells, the cadmium Sulphide (CdS)
was mostly used as a window layer [5,6]. (cds) mostly absorb bleu portion of sun light.
The fabrication and designing of low cost, high efficiency solar cell devices, selection of window material is
often important. Cadmium sulphide (CdS) is a low band gap ( Eg = 2.42 eV) n-type semiconductor and widely used
as window layer material in solar cell devices. CdS absorbs blue portion of solar spectrum and decrease in the
current density of solar cells [6, 7].
Mixed compound semiconductors like Cd(1-x)ZnxS, Cd(1-x)ZnxSe, CdSe(1-X)TeX, In1-xGaxSd1-yAsy have
potential applications in the fabrication of Photoconductive, Photovoltaic and Solar cells in the field of electronic
and optoelectronic devices[8,9]. These compounds have been prepared in thin film form by using sophisticated
techniques [10-11] to help the process of miniaturization of electronic devices.

International Conference on Condensed Matter and Applied Physics (ICC 2015)

AIP Conf. Proc. 1728, 020597-1–020597-5; doi: 10.1063/1.4946648
Published by AIP Publishing. 978-0-7354-1375-7/$30.00

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 EXPERIMENTAL DETAIL
The vast varieties of thin film materials are results of their deposition processing and fabrication techniques,
spectroscopic characterization and optical characterization probes that are used to produce the devices. It is possible
to classify these techniques in two ways namely physical process and chemical process.

Physical Process
Following physical processes are widely in practice.

Physical Vapor Deposition (PVD)

PVD processes proceed along the following sequence of steps:

a) The solid material to be deposited is physically converted to vapor phase;
b) The vapor phase is transported across a region of reduced pressure from the source to the substrate;
c) The vapor condenses on the substrate to form the thin film. The conversion from solid to vapor phase is done
through physical dislodgement of surface atoms by addition of heat in evaporation deposition or by momentum
transfer in sputter deposition. The third category of PVD technique is the group of so called augmented energy
techniques including ion, plasma or laser assisted depositions.

Evaporation

Evaporation or sublimation techniques are widely used for the preparation of thin layers. A very large number of
materials can be evaporated and, if the evaporation is undertaken in vacuum system, the evaporation temperature
will be very considerably reduced, the amount of impurities in the growing layer will be minimized. In order to
evaporate materials in a vacuum, a vapour source is required that will support the evaporant and supply the heat of
vaporization while allowing the charge of evaporant to reach a temperature sufficiently high to produce the desired
vapour pressure, and hence rate of evaporation, without reacting chemically with the evaporant.
To avoid contamination of the evaporant and hence of growing film, the support material itself must have a
negligible vapor pressure and dissociation temperature of the operating temperature. Laser beam evaporation has
also come in to use recently. The laser source is situated outside the evaporation system and the beam penetrates
through a window and is focused on to the evaporate material, which is usually fine powder form [12].

Sputtering

If a surface of target material is bombarded with energetic particles, it is possible to cause ejection of the surface
atom: this is the process known as sputtering. The ejected atoms can be condensed on to a substrate to form a thin
film. This method has various advantages over normal evaporation techniques in which no container contamination
will occur. It is also possible to deposit alloy films which retain the composition of the parent target material. DC
sputtering, radio frequency sputtering and magnetron sputtering methods are the oldest types of sputtering used [23].
High pressure oxygen sputtering and facing target sputtering are the two new methods introduced for deposition of
thin films for applications in superconducting and magnetic films.

Chemical Process
Among chemical and electrochemical methods the most important are chemical vapor deposition and Chemical
Bath Deposition.

Chemical Vapor Deposition

Chemical vapor deposition can be defined as a material synthesis method in which the constituents of vapor
phase react together to form a solid film at surface. The chemical reaction is an essential characteristic of this
method; therefore, besides. the control of the usual deposition process variables, the reactions of the reactants must

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be well understood. Various types of chemical reactions utilized in CVD for the formation of solids are pyrolysis,
reduction, oxidation, hydrolysis, synthetic chemical transport reaction etc.

Chemical Bath Deposition (CBD)

Among the chemical methods of thin film depositions, Chemical Bath Deposition (CBD) is probably the most
simplest method. The only requirements of these methods are a vessel to contain the solution (usually an aqueous
solution of common chemicals) and the substrate on which deposition is to be carried out. In addition to this various
complications such as some mechanism for stirring and a thermostated bath to maintain a specific and constant
temperature are options that may be useful. This rate control can be accomplished by generating the sulphide slowly
in the deposition solution. The rate of generation of sulphide, and therefore reaction, can be controlled through a
number of parameters, in particular the concentration of sulphide forming precursor, solution temperature, and pH.
Although CBD can be carried out both acidic and alkaline solutions, most of the CBD reactions have been carried
out in alkaline solutions.
Cd
NH3 42  Cd 2  4NH3 (dissociation of complex to free Cd2+ ions)

NH 2 2CS  2OH   S2  CN 2 H 2  2H 2 (formation of sulphide ions)
2
Cd  S2  CSd (CdS formation by ionic reaction)
nCd 2
 2nOH  Cd
OH 2 n (formation of a Cd(OH)2 cluster)
Cd
OH2 n  nS2  nCdS  2nOH (exchange reaction)

NH 2 2 CS  Cd  
NH 2 2 CS  Cd 
2 2


NH 2 2 CS  Cd 2  2OH   CdS  CN 2 H 2  2H 2 O

Cd
OH 2 n 
NH 22CS  nS 2  Cd
OH 2 
n 1
OH 2 Cd  S  C
NH 2 2
Cd
OH2 
n 1
OH2 Cd    S    C
NH 2 2  Cd
OH2 
n 1  CdS  CN 2 H 2  2H 2 O
1) The simple ion by ion mechanism:
[Cd(NH3)4]2+ Cd2+ + 4NH3 (dissociation of complex to free Cd2+ ions)
- 2-
(NH2)2CS + 2OH S + CN2H2 + 2H2 (formation of sulphide ions)
Cd2+ + S2 CdS (CdS formation by ionic reaction)
2) The simple cluster (hydroxide) mechanism:
nCd2+ + 2nOH [Cd(OH)2]n (formation of a Cd(OH)2 cluster)
[Cd(OH)2]n + nS2- nCdS + 2nOH (exchange reaction)
3) The complex decomposition ion - by - ion mechanism:
(NH2)2CS + Cd2+ [(NH2)2CS-Cd]2+
2+
[(NH2)2CS-Cd] + 2OH- CdS + CN2H2 + 2H2O
4) The complex decomposition cluster mechanism:
[Cd(OH)2]n + (NH2)2CS [Cd(OH)2](n-1) (OH)2Cd------S-----C(NH2)2
[Cd(OH)2](n-1) (OH)2Cd-----S----C(NH2)2 [Cd(OH)2](n-1) + CdS + CN2H2 + 2H2O
The last reaction continues until conversion of all the Cd(OH)2 to CdS. The first two mechanisms involved free
sulphide ions (or other anions). While the last two are based on breaking of a carbon-chalcogen bond and do not
involve formation of free chalcogenide [16].

Bath Temperature

The rise in bath temperature enhances the rate of diffusion and increases ionic mobility, hence the increase in
conductivity of the bath. The increase in temperature increases the rate of crystalline growth favoring the coarse
deposits. This increase in crystal size corresponds to decrease in polarization. At higher temperature, current
densities increase, which increases the rate of nucleation, hence fine-grained, smooth deposits can be obtained.

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 Current Density

At lower current densities (or over-potentials) the discharge of ions occurs slowly, so the growth rate decreases
but increases the crystallinity forming closely packed structures. As the current density is raised, the nuclei
formation rate will increase and the deposits become fine grained. At higher current densities, the rate of discharge
of ions becomes greater compared to rate of supply of ions and there is duplicity of ions near the cathode, which
favors the growth perpendicular to the substrate surface.

CHARACTERIZATION OF THIN FILM

Following methods are used to for characterization of thin films.

Thickness Measurement Using Weight Difference Method

Film thickness is an important parameter in the study of the film properties. Amongst different methods for
measuring the film thickness, the weight difference method is simple and convenient and thickness ‘t’ is measured
using the relation, t = m / A.ρb , where, ‘m’ is the mass of the film deposited on area ‘A’ of the substrate and ρ b is the
density of the material in the bulk form [17,18].

X- Ray Diffraction (XRD) Technique

X-ray diffraction (XRD) is a powerful technique for determination of crystal structure and lattice parameters.
The basic principles of X-ray diffraction are found in textbooks e.g. by Cullity [19], Diffraction in general occurs
only when the wavelength of the wave motion is of the same order of magnitude as the repeat distance between
scattering centers. This condition of diffraction is nothing but Bragg’s law and is given as,
2d sinθ = nλ, where, d = interplaner spacing, θ = diffraction angle, λ = wavelength of x-ray, n = order of diffraction.
If there is no inhomogeneous strain, the crystallite size, D, can be estimated from the peak width with the
K
Scherrer’s formula, D  , where λ is the X-ray wave length, B is the full width of height maximum of a
B cos  B
diffraction peak, B is the diffraction angle and K is the Scherrer’s constant of the order of unity for usual crystal.

Scanning Electron Microscopy (SEM)

Scanning electron microscope is an instrument that is used to observe the morphology of the solid sample at
higher magnification, higher resolution and depth of focus as compared to an optical microscope [25]. When an
electron strikes the atom, variety of interaction products are evolved.
The signals are transferred from point to point and signal map of the scanned area is displayed on a long
persistent phosphor C.R.T. screen. Change in brightness represents change of a particular property within the
scanned area of the specimen [21]. The scattering cross section for back-scattered electrons is given as [22],
2
Z  
Q  16.2  10  30   cot   , where, Z is atomic number and E is electric field. Here the cross-section is
E 2
proportional to Z2. Hence, the back-scattered electrons are used for the Z contrast or for compositional mapping.

Energy Dispersive Analysis by X-Rays Measurement (EDS)

In EDS technique a sample is made the target in an X- ray tube and is bombarded with electrons of suitable
energy, it emits characteristics X-rays. This is the basis of a method of chemical analysis. The emitted X-rays are
analyzed in an X-ray spectrometer and the elements present in the sample are qualitatively identified by their
characteristics wavelengths. For compositions greater than or about 1% and elements separated by few atomic
numbers, energy dispersion analysis is very useful because the intensities are increased about 100-Fold [26]. The
resolution however, of an energy dispersion instruments is as much as 50 times less than the wavelength dispersion
spectrometer using a crystal; thus overlapping of lines from nearby elements may occur.

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 TEM (Transmission Electron Microscopy)
A The transmission electron microscope (TEM) forms an image by accelerating a beam of electrons that pass
through the specimen. In TEM, electrons are accelerated to 100 KeV or higher (up to 1MeV), projected onto a thin
specimen (less than 200 nm) by means of the condenser lens system, and penetrate the sample thickness either
undeflected or deflected. The greatest advantages that TEM offers are the high magnification ranging from 50 to 106
and its ability to provide both image and diffraction information from a single sample.
The scattering processes experienced by electrons during their passage through the specimen determine the kind
of information obtained. . Elastic scattering involves no energy loss and gives rise to diffraction patterns. Inelastic
interactions between primary electrons and sample electrons at heterogeneities such as grain boundaries,
dislocations, second phase particles, defects, density variations, etc.

Electrical Conductivity
The use of thin films as resistors, contacts and interconnections has lead to extensive study of conductivity, its
temperature dependence, the effect of thermal processing stability and so on. Investigations of the electrical
resistivity as a highly structure sensitive properties make it possible to gain insight into the structural and electrical
properties of the metal film which is important from both the theoretical and practical point of view. The contact
techniques are most widely used for the measurement of resistivity. These techniques include two-point probe, four
point probe and the spreading resistance methods. The two-point method is simple and easy to use. In this technique
a constant current I is passed through a sample of known dimensions (cross-sectional area ‘A’). And the d.c. voltage
‘V’ between two fixed position probes (separation ‘d’) measured either with impedance voltmeter or
potentiometrically. For uniform sample resistively is given by ρ = (A/I) (V/d). In case of semiconducting thin films,
the resistivity decreases with increase in temperature. The thermal activation energies ‘Ea’ are calculated by using
the relation,  0 EXP
 E /
T  , where ‘E’ is the activation energy for the conduction ‘k’ is Boltzmann constant
and 0 is the pre exponential constant depending on the material.

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