CHAPTER 1

INTRODUCTION

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 1.1 Introduction

The definition of a thin film is one that considers the

contributing role of the surface region to the overall bulk properties
of the material (1). Thin films may be classified as (i) t < 100A,
ultrathin film (ii) t > 10,000A, thick film and (iii) 100A < t <
10,000A thin film. The scientific curiosity about the behaviour of two
dimensional solids has been responsible for the immense interest in
the study of the science and technology of thin films. Thin films
have made tremendous advances in the last decade, because of their
use in microelectronics, optical coatings, integrated optics, thin film
superconductivity, quantum engineering, communication and information
technology and solar cells. Using thin films, higher packing density,
higher speed performance and lower costs are obtained with decrease
in the size of the active electronic devices. In this thesis, a modest
attempt has been made to fabricate high quality thin films of ternary
chalcopyrite compounds viz. Copper Indium diselenide (CuInSe2, CIS),
Silver Indium diselenide (AgInSe2, AIS) and Copper Aluminium
diselenide (CuAlSe2, CAS) and their electrical, optical and structural
properties have been investigated.

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 1.2 Ternary chalcopyrite compounds

Many of the binary and ternary naturally occurring compounds

are known to exhibit semiconducting behaviour. Hahn et a1 (2) was
the first to synthesize the I-111-VI2 compounds in 1953. Goodman
and Douglas (3) discussed the possibility of semiconductivity in these
materials, a year later. CuInSez is one of the most promising
materials for thin film solar celis due to high absorption coefficient,
wide band gap range and easy conversion to n / p carrier type. The
efficiency of solar cells based on Cu(In, Ga)Sez has reached 17% as
reported by Tuttle et a1 (4). Laboratory-scale device efficiencies in
excess of 15% have been reported by several groups (5-7) for the
polycrystalline or amorphous CIS based cells. For integrated modules,
the maximum reported efficiencies are 11.2% for a 938 cm2 device
(8) and 10.4% for a 3883 cm2 array (9).
AgInSe2 is a material of special interest since it is a ternary
analog of CdSe which has been used in a number of electronic
devices. Although Cu-111-VI2 compounds have been studied extensively,
information on Ag-111-VI2 compounds is scarce. AgInSe2 is a direct
gap, n-type semiconductor with an energy gap of 1.19 eV (10) and
a melting point of 770C. AgInSez is quite sensitive to optical and
thermal stresses (11).
CuAlSe2 is a wide gap member of I-III-VI2 type chalcopyrite
semiconductors and it is a promising material for blue light-emitting
devices. It has a direct band gap of 2.67 eV at room temperature
(12, 13). However, it is difficult to grow high quality Cu-A1-VI2
compounds using conventional methods.

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 Ternary chalcopyrite crystals are of technological importance,
since they show promise for application in the areas of visible and
infrared light emitting diodes, infrared detectors and solar cells.

1.3 Structure of chalcopyrites

The I-111-VIz (ABC2) chalcopyrite phase possesses the tetragonal

structure, with four formula units per cell (14). The prototype phase
is the mineral chalcopyrite, CuFeS2. Each A- and B- atom is
tetrahedrally coordinated to four C- atoms, while each C- atom is
tetrahedrally coordinated to two A and two B atoms. If the cations
A and B were distributed at random, the cubic zinc blend structure
would result. Thus the chalcopyrite structure is a superlattice of the
zinc blend structure with c/a ratio approximately equal to 2. The
tetrahedral coordination implies that the bonding is primarily covalent
with sp3 hybrid bonds dominating. I-111-VIz compounds can be
regarded as the ternary analog of 11-VI binary compounds. They
can be derived from the binary phases by ordered substitution of
other group atoms so as to maintain an electron-to-atom ratio of
4. The ordered arrangement of metal atoms (or cations) lead to
the formation of tetragonal superlattice. When the zinc blend cell
is redoubled and the atoms of the cation sublattice are replaced
by A and B atoms, the ordered chalcopyrite structure is obtained.
The presence of two cations with different chemical properties introduce
two kinds of structural distortions, one geometrical (tetragonal
distortion) and the other crystallographic (internal distortion) (15).

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 The quantity 2-c/a is a measure of the tetragonal distortion which
may occur as a result of ordering. Thus the chalcopyrite structure.
is a member of the tetrahedrally coordinated structure family derived
from the well known sphalerite structure by isoelectronic and ordered
substitution of the bivalent zinc atom as given in figure 1.1. Neglecting
the sublattice distortion, all atom positions and bonding directions
are conserved, but the symmetry is reduced from cubic to tetragonal
by doubling the elementary cell. Tablesl.1 and 1.2 list the lattice
parameters and melting points of CuInSe2, AgInSe2 and CuAlSez.

Table 1.I Lattice parameters of I-111-VIz compounds

Ref.

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 Tablel2. Melting points of I-III-VI2 compounds

Compound Melting point Reference

O c

CuInSez 990 19

AgInSe2 770 19

CuAlSez 1200 20

Actually, the chalcopyrites are derived from the larger family

of compounds known as the adamantines. The adamantine family of
compounds (21) is made up of those compounds derived from one
or both of the tetrahedrally bonded diamond and lonsdaleite structures.
The four group IV elements C, Si, Ge and a - Sn possess the
structure, which consists of two interpenetrating fcc lattices arranged
so that each atom has four neighbours at the corners of a regular
tetrahedron. Formation of I-111-V12 compounds from tetrahedrally
co-ordinated group IV elements by substitution of elements so as to
maintain the electron-atom ratio equal to 4 is schematically shown
in figure 1.2. In order to explain the electronic structure of CuInSe2
and other compounds, one should take into account (i) the electronic
band structure (ii) the densities of states , (iii) the role played by

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 Fig.l.1.a. Sphalerite structure b. Chalcopyrite structure

Group IV elements
Si, G e

Group I1 - Group VI
ZnSe

Group I - Group I11 - Group VI

CuInSez
Fig.l.2. Schematic diagram of formation of
I-111-VI2 compounds from group IV elements

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 the copper atom d orbitals and (iv) the energy band gap and t h e
valence band splittings. The s and p states give a maximum of 4
valence states for each value of n. When atoms form covalent bonds
in a crystal, we get a set of states directed from one atom towards
its nearest neighbours using hybridized orbitals. The energy in excess
required to form hybridized bonding orbitals is obtained by the
overall decrease in crystal energy. Actually, the number of orbitals
is conserved during hybridization and Ebond < Enon bond < Eorbital.
'ns' and 'np' valence electrons are the principal contributors to the
covalent bond. The presence of d electrons as in copper make the
valence levels mixed. As a result pd hybridization occurs and will
affect the electronic structure resulting in the band gap shrinkage
and minimization of spin-orbit valence band splitting as in CuInSez.
The band gap shrinkage in CuInSez can be assigned to non-ideal
anion position as detected by mismatch in classical atomic radii. The
calculation on electronic charge density for states in the upper valence
band show that for CuInSez, Cu-Se contact appears covalently bonded
with a significant ionic component, whereas the In-Se contact appears
to be non-bonding 1221. The In atom merely fills up the space
without forming a strong bond with the selenium atom. The weaker
In-Se bonding compared to the Cu-Se bond forms substitutions at
the In site rather than the copper site with relative ease. Thus the
valence stoichiometry is controlled by the copper vacancy formation
and subsequent substitution by indium.

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 1.4 Phase behaviour and defects in I-111-VI2 compounds

In I-111-VI2 compounds, defects are caused by vacancies (empty-

lattice sites), interstitials (atoms present on sites where they should
not be) and site interchanges by atoms (atom A on the site of B).
These defects break up the lattice periodicity which in turn diminish
the carrier mobility. Also the Fermi level is modulated by the
presence of these defects induced by variations in sublattice cation
ordering or due to non-stoichiometry. The ternary compounds show
two types of non-stoichiometry. One is due to the solid solution
and the other involves an excess or deficiency of electrons compared
to the number needed to make all bonds. The former can be reduced
by precipitation of minor phases (CuxSe, InySe) present in the
compound CuInSe2. Defects are formed by the vacancies, interstitials
and inter change of sites. The absence of room temperature mutual
solubility of 12-VI and I-111-V12 type compounds is caused by the
crystallo-chemical difference between the compounds. The 12-VI type
compounds have only n = 2.66 electron/atom, while I-111-VI2 type
compounds have n = 4 electron/atom. The VI anions have more
than 4 neighbours, resulting in a deficiency of electron to form
saturated homopolar sp3 bonds. In addition to the binary extremas
on the In2Se3-Cu2Se tie line, several copper poor phases of CuInSez
have been identified and studied. The compounds are Cu2InqSe7,
Cu3IngSe9, CuIn3Se5, CuIngSes, CusInSe4 (23, 24, 25, 26, 27). Any
phase along with the CuInSe2 phase will produce deviation from the
ideal chalcopyrite behaviour. It should also be noted that the presence

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 Tablel.3. Assignment of defect levels in CuInSez

Sample Ionization energies (meV)

type

V - vacancies i - interstitials

of oxygen plays an important role in the stability of Cu-Se and

In-Se binary secondary phases. The presence of these phases modulate
the activation energy and optical band gap of the chalcopyrite

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 phase. A summary of the possible assignments of donor and acceptor
levels observed in CuInSez for different deviations from molecularity
and valence stoichiometry are given in Tablel.3 from an earlier report
* (28). Thus these defects play an important role in determining the

opto-electronic, microstructural ,and phase behaviour of I-111-VIz

compounds.

1.5. Earlier studies on I-111-VI2 compounds

In crystallography, the diamond structure is one of the simplest

and most symmetrical arrangement of atoms. Only silicon and

germanium crystallize in this structure. Grimm-Sommerfeld rule of

chemical bonding accounts for the semiconducting behaviour, change
in band gap and thermal conductivity of these elements. In ternary
compounds which are semiconducting, the drop in symmetry due to
superlattice formation opens the way for non-linear devices and
interesting optical properties. A detailed study on the chalcopyrite

structure, growth, luminescent studies, non-linear optical properties,

electrical-transport properties of I-111-VI2 and 11-IV-VIz compbunds
has been done by Shay et a1 (14). Zhuze et a1 (19) have given a
systematic investigation on the electrical properties of semiconducting
compounds with the general formula ABC2 and have studied the

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 general relationships between electrical properties and the chemical
bond nature. Temperature dependence of electrical conductivity of
CuInSe2, bulk carrier mobility, thermoelectric power and band gap
are studied. A detailed study on I-111-VI2 compounds grown under
minimum VI element pressure or annealed under maximum VI element
pressure has been given in an earlier paper (29). Room temperature
electrical properties of ten compounds of I-111-V12 family are discussed.
Band gap value, absorption edge, conductivity type, carrier mobility,
carrier concentration for the compounds are investigated in ,this paper.
In a short communication by Elliot et a1 (30), some electrical properties
of flash evaporated CuInSe2 thin films are reported. The composition,
morphology and crystallographic structure of chemical bath deposited
CuInSez thin films are studied by Padam (31). A detailed study on
the electrical and optical properties of flash evaporated p-CuInSez
thin films is done by Sridevi and Reddy (32). Temperature dependence
of conductivity and optical absorption corrected for background
absorption for CulnSez thin films are also reported here. Structural,
optical and electrical properties of spray pyrolitically deposited CuInSez
thin films are reported by Tembhurkar and Hirde (33). Plot of
conductivity versus temperature, dependence of absorption coefficient a
with photon energy hu and carrier mobility values are also given.
Electrical conductivity studies on both p- and n-type bulk CuInSez
have been done by Parkes et a1 (34). A detailed study on the
vacuum deposited p- and n-type CuInSez thin films has been done

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 in an earlier work (35). Varela et a1 (36) have made electrical

conductivity studies of polycrystalline thin films of CuInSez. Dependence

of electrical and optical properties of CuInSez thin films on the

composition has been done by Tuttle et a1 (37). The effect of substrate

temperature on these properties. is also investigated. Electrical and
luminescent properties of bulk CuInSez are studied by Migliorato et

a1 (38). The properties are studied on bulk CuInSez grown in various

selenium pressures. Electrical properties of some I-III-VIz chalcopyrite
compounds grown by solid state growth method are reported by

Ashida et a1 (39) in a recent work. In another paper (40), they

report the effect of annealing on the electrical and structural properties

of quasi flash evaporated CuInSe2 thin films. Recently, Schmidt et

a1 (41) report the electrical, optical and structural properties of

co-sputtered CuInSe2 thin film. Variation of activation energy and

band gap with compositions for solution grown non-stoichiometric

CuInSez thin films is investigated by Sharma and Garg (42). Dependence

of Hall parameters on temperature for CuInSez single crystals is
reported by Horig et al (43). Optical ban
CuInSe2 thin films is reported by Neu

work. A detailed study on the electri

properties of some I-III-VI2 compoun

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 12

vacuum evaporation has been done by Kazmerski et a1 (45). Temperature

dependence of the absorption edge for CuInSe2 has been investigated

by Horig et a1 (46). Structural and optical properties of spray

pyrolitically deposited CuInSe;! thin films are studied. by Agnihotri

et a1 (47). Influence of impurities and free carriers on the optical

properties of CuInSez thin films has been done by Sobotta eet a1

(48). Reflection and transmission spectra of laser deposited CuInSez

thin films are studied by Kindyak et a1 (49). Optical transitions
associated with the conduction band is studied in this paper. Infrared
optical characterization of thermally oxidized CuInSe;! thin films has
been done by Sobotta et a1 (50). The vibrational modes associated
with this compound are studied in detail. Varela et al (51) investigate
the dependence of refractive index and absorption coefficient on
the Cu-In percentage ratio.

Studies on the electrical and optical properties of AgInSe;!

single crystals have been done in detail by Lerner (17). The values
of thermal and optical band gap are given. Electrical and photoelectrical
properties of chalcopyrite semiconductor AgInSe2 are reported by

Navdeep Goyal (11). The optical properties of AgInSez thin films are

given by Abdelghany et a1 (52).

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 Preparation and properties of single crystal CuAlSe2 is reported
by Honeyrnan (18). Electrical conductivity, optical absorption and
photoconduction are also investigated in this paper. Raman studies

on CuAlSe2 are reported by Chichibu et al (53, 54). Photoluminescence

studies in CuAlSe2 epilayers grown by low- pressure MOCVD on

GaAs substrates are also investigated (55).

More detailed studies and reported values of various parameters

of chalcopyrite films deposited by various methods will be discussed
in the course of the thesis.

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