Study of SILAR deposited ZnO for

Inverted Organic Solar Cells

Dissertation

Submitted in partial fulfillment of

the requirements for the award of degree of

Master of Technology
in
Energy Systems Engineering

Submitted by
Pradeepkumar Podal
(08317005)

Under the guidance of

Prof. Manoj Neergat

Department of Energy Science and Engineering
Indian Institute of Technology Bombay
2010
 Declaration

I declare that this written submission represents my ideas in my own words and where others'
ideas or words have been included, I have adequately cited and referenced the original
sources. I also declare that I have adhered to all principles of academic honesty and integrity
and have not misrepresented or fabricated or falsified any idea/data/fact/source in my
submission. I understand that any violation of the above will be cause for disciplinary action
by the Institute and can also evoke penal action from the sources which have thus not been
properly cited or from whom proper permission has not been taken when needed.

_________________________________

Pradeepkumar J. Podal
08317005

Date: 02 July 2010

Abstract

Organic Solar Cells (OSCs) are a new generation of solar cells based on conjugated polymers
and fullerene derivatives. A blend of poly(3-hexyl-thiophene-2,5-diyl) (P3HT) and [6,6]-
phenyl-C61-butyric acid methyl ester (PCBM) is a popular material system to implement
these devices. Although OSCs are very economical to fabricate and have many advantages,
such as light weight, flexibility and semi-transparence, they suffer from low efficiency and
stability issues. A new architecture called inverted OSC allows cells with higher lifetimes and
generally uses ZnO as a transparent electrode. In order to achieve commercial deployment of
OSCs it is necessary to deposit all its constituent layers by low-cost processes. Hence it has
been attempted to deposit a ZnO layer using an economical and scalable chemical process
called SILAR and to study its suitability for use in the inverted OSC. The deposited ZnO
layers were characterized for their optical, electrical and morphological properties. Also non-
inverted OSCs were fabricated to study their performance.

Keywords: SILAR, ZnO, inverted architecture, organic solar cells

Table of Contents

List of Figures ..................................................................................................... iv

Nomenclature ...................................................................................................... vi

1. Introduction .................................................................................................. 1
1.1 Motivation .................................................................................................................... 2
1.2 Objective and Layout of the report ................................................................................ 3
2. Basics of Organic Solar Cells ....................................................................... 5
2.1 History ......................................................................................................................... 5
2.2 Device Physics ............................................................................................................. 6
2.2.1 Origin of Band Gap ................................................................................................ 6
2.2.2 Excitons ................................................................................................................. 7
2.2.3 Working principles ................................................................................................. 7
2.3 Materials ...................................................................................................................... 9
2.3.1 Donors ................................................................................................................... 9
2.3.2 Acceptors ............................................................................................................. 12
2.4 Architecture ................................................................................................................ 13
2.4.1 Metal Insulator Metal (MIM) or Homojunction Solar Cells .................................. 13
2.4.2 Planar Heterojunction (PH) Solar Cell .................................................................. 13
2.4.3 Bulk Heterojunction (BH) Solar Cell .................................................................... 15
2.4.4 Tandem or Multi Junction Solar Cell .................................................................... 15
2.4.5. Inverted Architecture ........................................................................................... 16
3. Non-inverted organic solar cells ................................................................ 19
3.1 Experimental Details .................................................................................................. 19
3.1.1 Substrate Preparation............................................................................................ 19
3.1.2 ITO Patterning ..................................................................................................... 20
3.1.3 Application of PEDOT:PSS layer ......................................................................... 21

ii
 3.1.4 Active layer deposition ......................................................................................... 21
3.1.5 Metallization ........................................................................................................ 22
3.1.5 Encapsulation. ...................................................................................................... 23
3.2 Characterisation and Discussion ................................................................................. 24
4. Successive Ionic Layer Adsorption and Reaction deposition of ZnO ...... 26
4.1 Background ................................................................................................................ 27
4.1.1 SILAR Deposition ................................................................................................ 27
4.1.2 Advantages of SILAR .......................................................................................... 28
4.2 Experimental details ................................................................................................... 29
4.2.1 Preparation ........................................................................................................... 29
4.2.2 Deposition ............................................................................................................ 30
4.2.3 Measurements ...................................................................................................... 30
4.3 Results and discussion ................................................................................................ 31
4.3.1 Thickness measurements ...................................................................................... 32
4.3.2 XRD Analysis ...................................................................................................... 33
4.3.3 SEM and Optical images ...................................................................................... 36
4.4.4 Spectrophotometry ............................................................................................... 39
4.4.5 Hall Effect measurements ..................................................................................... 40
5. Conclusion and Future Work .................................................................... 44
5.1 Conclusions ................................................................................................................ 44
5.1.1 SILAR ................................................................................................................. 44
5.1.2 Non-Inverted OSC ............................................................................................... 45
5.2 Future work ................................................................................................................ 45
References ....................................................................................................... 47
Acknowledgements ......................................................................................... 52

iii
List of Figures

Fig. Title Page

No
1.1 Requirements to be satisfied by organic solar cells before commercialization 3

2.1 Photo induced charge transfer from P3HT to PCBM 9

2.2 Hole conducting p-type donor polymers MDMO-PPV, P3HT and PFB 10

2.3 Band diagram of polarized co-polymers 11

2.4 Chemical structure of PCPDTBT a low band gap copolymer thiophene 11

2.5 Electron conducting acceptor polymers CN-MEH-PPV, F8TB and a soluble 12

derivative of C60, PCBM

2.6 Symmetrical structure of Fullerene 12

2.7 Molecular structure of [70] PCBM 12

2.8 Bilayer heterojuntion organic solar cell architecture 14

2.9 Bulk heterojuntion organic solar cell architecture 15

2.10 Simplified energy band diagram of a series-connected tandem bulk 16

heterojunction solar cell

2.11 Normal and inverted architectures of organic solar cell 17

2.12 Energy level diagram of the different layers in an inverted organic solar cell 18

3.1 Design of a offset printed mask used for ITO patterning 20

3.2 Layout describing the active layer of Organic Solar Cell 23

3.3 An ITO|PEDOT:PSS|P3HT:PCBM|Al layered bulk heterojunction organic 23

solar cell fabricated in IIT Bombay

3.4 J-V Curves of fabricated organic solar cells in dark and under illumination 24

3.5 Equivalent circuit of an organic solar cell 25

iv
4.1 Schematics of thin film growth during one SILAR cycle 28

4.2 The average growth rate of ZnO film for different SILAR process 33

4.3 XRD patterns of films deposited with and without sonication 34

4.4 Optical image (100x) of ZnO deposited using L0 process on glass substrates 36

4.5 Low (a) and Magnified (b) SEM images of ZnO films deposited using 37
sonication assisted SILAR

4.6 Low (a) and Magnified (b) SEM images of ZnO films deposited without 38
sonication in SILAR

4.7 Total and Normal transmission pattern of deposited ZnO films 39

4.8 Comparision of (a) carrier concentration, (b) mobility and (c) resistivity of 41
ZnO films obtained by different SILAR processes

4.9 Comparision of (a) carrier concentration, (b) mobility and (c) resistivity of 42
ZnO films obtained by different doping concentration

v
Nomenclature

BH Bulk heterojunction

D-A Donor-Acceptor

FF Fill factor

HOMO Highest Occupied Molecular Orbital

ITO Indium Tin Oxide

LUMO Lowest Unoccupied Molecular Orbital

MDMO-PPV (poly[2-methoxy-5-(3,7-dimethyloctyloxy)]-1,4-phenylenevinylene)

MIM Metal Insulator Metal type Device

OSC Organic Solar Cell

P3HT (poly(3-hexylthiophene-2,5-diyl)

PCBM [6,6]-phenyl-C61-butyric acid methyl ester

[poly [2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b’]dithiophene)-alt-
PCPDTBT 4,7(2,1,3-benzothiadiazole)]

PEDOT:PSS poly(3,4-ethylene dioxythiophene): poly(styrenesulfonate)

(poly (9,9’-dioctylfluorene-co-bis-N,N’-(4-butylphenyl)-bis-N,N’-phenyl-
PFB
1,4-phenylenediamine).

PH Planar heterojunction

RCA Radio Corporation of America

SILAR Successive ionic layer adsorption and reaction

TCO Transparent conducting oxide

ZnO Zinc oxide

vi
Chapter 1

Introduction

Interest in the renewable sector has grown enormously in the last few years due to the
emphasis on environmental and climate change issues. Besides this, reports claim that with
status quo conditions, known reserves of petroleum would be depleted in the next 50 years
and coal will last for only about 200 years [1]. Realising the fact that sooner or later, the globe
is eventually going to run out of coal and gas, most governments are focusing on growth of
alternative sources of energy.

Solar photovoltaics (PV) is bound to play a major role in this global change as can be
seen in the growth of photovoltaic installations from 400 MW in 2001 to 7.4 GW in 2008 [2].
Currently crystalline Si consists around 85% of both the installed and production capacity of
PV industry while the rest of it is based on thin film technology [2]. Although amorphous Si
almost completely covers the thin film market there has been a recent growth in acceptance of
2nd generation Cadmium Telluride (CdTe) and Copper Indium Gallium Selenide (CIGS)
 TM
based thin film solar cells. First Solar , the market leader in both thin film and CdTe based
solar cells will reach an annual production capacity of more than 1 GW by the end of 2009
[2].

PV prices have reduced greatly over the last 20 years to approximately $2.8/W-peak in
2009. However, in spite of this, the PV market still largely remains an incentive-driven
industry with 95% of sales stimulated by government sops [3]. Thus the holy grail of the PV
industry is to reduce the price per watt-peak of the produced power, so as to achieve grid
parity and reduce its dependence on any incentives. The newer thin films seem promising but
these technologies suffer from different issues. Cadmium is a toxic carcinogen and can cause
serious environmental hazards in case of improper disposal of the CdTe based solar cells [4],
whereas indium which is a prime component of the CIGS technology has limited reserved on
earth and is expected to become costly with increase in demand.

Owing to the above mentioned issues and opportunities a third generation of solar
cells with totally different materials is being intensely followed by the scientific community
and is getting ready for commercialisation. Called as organic solar cells, these devices use
“small molecules” [5] or “conjugated polymers” [6] as their main components. However, due
to the advantages offered by the conjugated polymers in processing, they have currently
overtaken small molecules as the preferred candidates for organic solar cells.

1.1 Motivation

Organic solar cells are a new generation of light weight, flexible solar cells with
promise of very low cost roll to roll fabrication. The polymers used in fabrication of organic
solar cells are soluble in most organic solvents allowing them to be solution processed. This
makes it possible to print the cells using an inkjet printer or other offset printing techniques
considerably bringing down the fabrication cost. Due to such roll to roll processing, OSCs
have one of the highest energy amortization (difference between the energy expended to
harvest an energy source and the amount of energy gained from that harvest) values. They are
light and can be also printed on flexible surfaces opening up new avenues not generally
possible for their traditional inorganic counterparts.

2
 Another major advantage is the bio-degradability of the conjugated polymers used in
OSCs making them environmentally benign. The films can have semi-transparence and
choice of colour. Hence, along with their flexibility, it is easier to incorporate OSCs into
existing products without affecting or even improving their aesthetic value. One of the lesser
quoted advantage of the OSCs is their absorption only in specific frequency bands unlike
inorganic materials which absorb all frequencies of solar spectrum above their band gap. This
allows multi junction OSCs to effectively absorb any radiation reflected from the non
illuminated end making them more efficient in multi junction architectures.

With all the above mentioned advantages and lower price of manufacturing, organic
solar cells (OSC) seem to be a very promising. However, in order to be commercially feasible
they need to satisfy the triple requirements as depicted in Fig. 1.1. Although OSCs can easily
satisfy the economic requirement, they have comparatively limited efficiencies and stability.
One of the methods to increase the stability is to use an inverted architecture [7] which has
been described later and has a major emphasis in this report.

Fig. 1.1 Triple requirements to be satisfied by organic solar cells before commercialization.

1.2 Objective and Layout of the report

The purpose of the current work was to fabricate and study organic solar cells. One
main focus area is deposition of doped zinc oxide (ZnO) layer using successive ionic layer
adsorption and reaction (SILAR) process. ZnO, when used as a transparent conducting oxide

3
(TCO) can be used to fabricate inverted organic solar cells, which as mentioned earlier can
improve the lifetime of organic solar cells.

Chapter 2 describes the basics of organic solar cells, its history, device physics and the
various architectures including the inverted one.

Chapter 3 enlists the methodologies used in fabrication of the organic solar cells and
the device characterisation.

Chapter 4 describes the SILAR process, its advantages and its study as a ZnO
deposition technique to be use as a TCO with inverted organic solar cell.

Chapter 5 finally sums up this report with conclusion and the recommended future
work

4
Chapter 2

Basics of Organic Solar Cells

This chapter provides a brief introduction to the history, device physics and the
various architectures of organic solar cells.

2.1 History

OSCs were studied as early as 1959 with the fabrication of anthracine based organic
solar cell by Kallman and Pope [8]. However, these cells showed extremely low efficiencies.
Many subsequent efforts to develop higher efficiency solar cells based on a single layer
(called homo-junction devices) were unsuccessful mainly due to the low dielectric constant of
organic materials (typically 2 to 3). Because of the low dielectric constant, absorption of
incident radiation did not lead to formation of free charge carriers in organic materials like
their inorganic counterparts. The small electric field formed between the organic material and
their charge collecting metal electrode was not sufficient to dissociate the excitons (photo-

5
excited electron hole pairs bound by electrostatic attraction) to form free charge carriers and
thus only low efficiencies could be obtained.

It was not until 1986 that a major breakthrough was achieved by C. W. Tang who used
a heterojunction made up of two materials to fabricate a solar cell with an efficiency of about
1% [9]. The novel idea was to use a high electron affinity organic material to extract the
electron from an exciton. The next major advancement was the bulk heterojunction
architecture where instead of using two separate layers of different materials, their
interpenetrating blend was used [10]. This allowed increasing the thickness of the light
absorbing active layer and efficiency close to 5% was achieved. Subsequently cells based on
low band gap materials and multi junction cells (tandem solar cells) were fabricated capable
of absorbing a wider spectrum leading to an efficiency of 7.9%, highest recorded till now as
of 2010 [11].

2.2 Device Physics

2.2.1 Origin of Band Gap

In inorganic semiconductors such as silicon the band gap is produced mainly due to
the crystalline nature of the material. Presence or absence of electron (depending on doping)
causes either an extra electron or electron deficiency in the crystalline structure. This gives
rise to a band gap between the free and the bonded electrons and thus semi conductivity.

Unlike silicon, organic materials are not crystalline to have a characteristic band gap.
However, the conjugated polymers consist of alternate single and double bonds formed by the
sp2 hybridized orbitals of the carbon atoms. The σ bonds forms the main backbone of the
polymer whereas the π bonds are formed by overlapping of out of plane p z orbitals. These π
bonds are delocalized over the entire molecule and are responsible for the conductivity
observed in conjugated polymers. For single and double bonds of equal length, the polymer
would have a half filled pz band and a metallic character. However due to Peierl’s instability
the backbone dimerises into longer single bonds and shorter double bonds creating two
distinct degenerate states from the half filled pz band, a bonding π orbital and an anti-bonding
π* orbital [12, 13]. The anti-bonding orbital is at a higher energy and forms the LUMO

6
(Lowest Unoccupied Molecular Orbital) band whereas the lower energy bonding orbital
forms the HOMO (Highest Occupied Molecular Orbital) band leading to creation of a band
gap in polymers. The LUMO and HOMO are analogous to conduction and valence bands of
inorganic semiconductors and are formed due to aggregation of the discrete HUMO and
LUMO levels of the molecules in the polymer chain. This band gap is in the range of 1.5 to
3 eV which makes them an ideal fit for use in visible optical light range [12].

One important difference between organic semiconductors and their inorganic

counterparts is the low mobility of charge carriers (around 0.1 cm2/ Vs) in organic materials;
however, this is compensated by their high absorption coefficients (usually > 105/cm) [12].

2.2.2 Excitons

The photo conversion mechanism in organic solar cells is fundamentally different

from the inorganic ones. In inorganic solar cells, free electron hole pairs are produced upon
illumination. Excitons generated under light in materials like silicon are easily dissociated by
available thermal energy into free charge carriers due to their small binding energy. However,
excitons in organic solar cells, as mentioned earlier, cannot be spontaneously dissociated at
room temperature due to their large binding energies (0.1 to 1 eV) [12]. In order to collect any
current from these solar cells the excitons need to be disassociated first to form free charge
carriers.

The best method to separate the excitons is by making a heterojunction as used by

Tang [9], where the difference in the LUMOs of the donor and acceptor molecules help in the
dissociation. The mechanism and the materials involved have been described in detail in the
following sections.

2.2.3 Working principles

The complete process from light illumination on an organic solar cell to electron
availability for the external circuit of the solar cell can be broken down into the following
stages:

7
 1. Generation of exciton

An incident photon provides enough energy for the transition of an electron from the π
to π* orbital of the organic molecule and gives rise to an excited electron-hole pair, the
exciton.

2. Diffusion of exciton to charge separation interface

These excitons diffuse through the material under concentration gradient to the charge
separation interface generally the donor-acceptor (D-A) interface.

3. Exciton dissociation into free charge carriers

As described above the difference between the energy bands of donor and acceptor
materials provide enough energy for the dissociation of exciton into separate charge
carriers.

4. Migration of free charge carrier to corresponding electrode.

These charge carriers migrate under the influence of the electric field created due to
the difference between the work functions of the electrodes to produce the external
current.

The external quantum efficiency (EQE) can be expressed based on these steps as

ȠEQE = ȠA x ȠED x ȠCT x ȠCC

where ,

ȠA : Absorption efficiency [ No of photo generated excitons/ Number of incident photons ]

ȠED : Exciton Diffusion Efficiency [ No of excitons diffusing to DA interface/Number of photo

generated excitons]
ȠCT : Charge transfer efficiency [No of excitons dissociated at the DA interface/Number of
excitons diffusing to the D-A interface]
ȠCC: Carrier Collection Efficiency [No of free charge carriers at the electrodes/Number of
excitons dissociated at the D-A interface]

Fig. 2.1 shows transfer of an excited electron from the donor (P3HT) to the acceptor molecule
(PCBM) along with the energy levels.

8
Fig. 2.1. Photoinduced charge transfer. After excitation in the thiophene polymer the electron is
transferred to the PCBM molecule with higher electron affinity represented by the energy band
diagram.

2.3 Materials

There are two main requirements for the materials used in organic solar cells,
generation of excitons on illumination and transportation of dissociated charge carriers.
Besides this the materials should have adequate difference in their electro-negativity to effect
the dissociation of the excitons. Some of the commonly used organic materials which satisfy
these requirements and are used as donors and acceptors in OSCs have been described below.

2.3.1 Donors

The donor type polymers are those with low electronegativity and thus have a
tendency to lose their excited electrons to more electronegative acceptor layers in donor
acceptor blends. The donors after losing their electrons act as good hole conducting layer
whereas the acceptor materials act as electron conducting layer. One of the most important
hole conducting polymer widely used today in fabrication of organic solar cells is
P3HT (poly (3-hexylthiophene-2,5-diyl) shown in Fig. 2.2. Various other donors like
MDMO-PPV (poly[2-methoxy-5-(3,7-imethyloctyloxy)]-1,4-phenylenevinylene) and PFB

9
(poly(9,9’-dioctylfluorene-co-bis-N,N’-(4-butylphenyl)-bis-N,N’-phenyl-1,4-
phenylenediamine) used traditionally have been abandoned in favour of more efficient and
stable P3HT [14,15]. It should be noted that only regioregular P3HT is capable of achieving
the required crystallinity and hence mobility essential for efficient OSCs.

Fig. 2.2 Hole conducting p-type donor polymers MDMO-PPV (poly[2-methoxy-5-(3,7-

dimethyloctyloxy)]-1,4-phenylenevinylene), P3HT (poly(3-hexylthiophene-2,5-diyl) and PFB
(poly(9,9’-dioctylfluorene-co-bis-N,N’-(4-butylphenyl)-bis-N,N’-phenyl-1,4-phenylenediamine).

In order to further improve the efficiency, low band gap materials have been
engineered and are increasingly used now-a-days. The low band gap is achieved by using co-
polymers based on alternating donor and acceptor structures and increasing the double bond
character between the donor and acceptor molecules. This causes transition dipoles at the
donor-acceptor bonds and a resulting field pointing towards the acceptor. Consequently, the
excited electron jumps from the HOMO of the donor to LUMO of the acceptor rather than its
own, thus reducing the band gap as shown in Fig. 2.3. Note that the donors and acceptors
terms used here do not refer to the donor and acceptor in the solar cell but within the donor
co-polymer material.

10
Fig. 2.3 Polarized co-polymers which cause the excited electrons to jump from the HOMO of the
donor to LUMO of the acceptor reducing the bandgap. Donors and acceptors terms used here don’t
refer to the donor and acceptors in the solar cell but within the donor co-polymer material.

Fig. 2.4 Chemical structure of PCPDTBT [poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-

b’]dithiophene)-alt-4,7(2,1,3-benzothiadiazole)] a low band gap copolymer thiophene [16]

Co-polymers like PCPDTBT [poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-

b;3,4-b’]dithiophene)-alt-4,7(2,1,3-benzothiadiazole)] shown in Fig. 2.4 with an optical
bandgap of Eg ~1.4 eV [16] appears to be one of the new materials which may play an
important role in the future of organic photovoltaics.

11
2.3.2 Acceptors

Fig. 2.5 shows the most commonly used acceptors in OSCs. However much like
P3HT, its donor counterpart, fullerene derived PCBM ([6,6]-phenyl-C61-butyric acid methyl
ester) has emerged as the most favourable choice as the acceptor material. Unlike other
acceptor materials or fullerene is not a polymer, but its electronic structure and optical
properties are very well suited for use in OSCs. PCBM makes a great acceptor because a
single molecule C60 can accept up to six electrons and the added functional group allows it to
be soluble in most organic solvents and hence solution processed [12].

Fig. 2.5 Electron conducting acceptor polymers CN-MEH-PPV (poly-[2-methoxy-5-(2’-

ethylhexyloxy)-1,4-(1-cyanovinylene)-phenylene) and F8TB (poly(9,9’-dioctylfluoreneco-
benzothiadiazole) and a soluble derivative of C60, PCBM ([6,6]-phenyl-C61-butyric acid methyl
ester) [12].

Fig. 2.6. Symmetrical structure of Fullerene. Fig. 2.7. Molecular structure of [70] PCBM.

The exact band gap of PCBM is still under debate due to its complicated electronic
structure but optically an absorption band gap of 1.6 eV have been observed [17]. This being

12
the optimum value for single junction photovoltaic devices, PCBM contributes significantly
to the absorption of the spectrum in P3HT:PCBM based solar cells. However C 60 and its
derivatives like PCBM have low absorption in the visible region of the spectrum due their
high degree of symmetry as shown in Fig. 2.6 which makes low energy transitions forbidden.
Compared to C60 lesser symmetrical C70 shown in Fig. 2.7 is capable of a wider absorption
spectrum and hence can achieve higher efficiencies. Use of [71]-PCBM have shown a 44%
higher efficiency close to 6% compared with [61]-PCBM [18] when blended with PCPDTBT.

2.4 Architecture

As described earlier organic solar cells have come a long way from a modest
efficiency of 0.1 % in 1959 to close to 8% in 2010. Following are the various generations in
the development of these devices.

2.4.1 Metal Insulator Metal (MIM) or Homojunction Solar Cells

The first generation organic solar cells were based on Metal Insulator Metal type
architecture. Here an organic conjugated polymer like MEH-PPV [poly( 2-methoxy,5-( 2’-
ethyl-hexoxy)-1,4-phenylenevinylene)] was sandwiched between two conductors like Al and
ITO (Indium Tin Oxide) with different work functions. The difference between the work
function of electrodes leads to an evenly distributed electric field within the polymer. Any
photo-generated charge carriers drifted under the influence of this electric field towards the
electrodes.

Since the field produced by the difference in work functions of the electrodes is not
sufficient to dissociate all the excitons into free charge carriers, efficiency of such
homojunction MIM devices was very low, around 0.1%.

2.4.2 Planar Heterojunction (PH) Solar Cell

An improvement in the efficiency of OSCs occurred with the development of planar

heterojunction (PH) solar cells as shown in Fig. 2.8. These devices consist of donor and

13
acceptor material stacked in the planar layer. Upon illumination, excitons are generated and
separated in these devices under the influence of the potential difference between the donor
and acceptor bands. The acceptor materials have higher electron affinity compared to the
donors. When illuminated electrons are excited from HOMO to LUMO in the donor material
and then pulled away to the LUMO of acceptor due to its higher ionization potential. The
energy released by the electron in this transfer provides the energy for charge separation. In
this kind of solar cell Ƞ CT and ȠCC approach unity because once the excitons reach the DA
interface they are easily separated and since the holes and electrons travel through different
materials their recombination is not possible.

Fig. 2.8 In bi-layer devices charge carriers can dissociate at the D-A interface and hence the thickness
of the active area is limited by the exciton diffusion length [12].

In addition to the energy gap between LUMO of donors and acceptors, there also
exists an interfacial dipole between the donor and the acceptor phases [12] which further
assists the charge separation by repelling the charge carriers and avoiding their recombination.
Both the donor and acceptor materials are attached to metal electrodes with suitable work
functions corresponding to their HOMO and LUMO respectively.

ȠED is dependent on the width of the donor layer as excitons have diffusion lengths of
less than 100 Ao and any further increase in the donor layer thickness leads to reduced
efficiency. At the same time, ȠA decreases for small donor layer thickness since the optical
absorption length for the organic polymers is greater than 1000 A o. Hence an optimum trade
off has to be achieved between ȠED and Ƞ A for the donor thickness. Efficiencies of around 1%
were achieved for such planar heterojunction devices [9].

14
2.4.3 Bulk Heterojunction (BH) Solar Cell

A further improvement in the solar cell efficiency occurred with the development of
bulk heterojunction (BH) solar cells. The main issue with the PH architecture was that Ƞ ED
and Ƞ A were not independent and any increase in the absorption region led to exciton
annihilation. In order to solve this, the BH cell consists of a nanometre scale interpenetrating
network of donor (D) and acceptor (A) molecules sandwiched between a transparent
conducting oxide like ITO and an Al metal electrode as shown in Fig. 2.9. This makes it
possible for almost all the excitons generated to reach a D-A interface within its diffusion
length and ȠED approaches unity. As a result of this Ƞ A can be tuned independently of ȠED.

However since the charge carriers have to cross the entire bulk layer before they can
make into the electrodes ȠCC might decrease. In order to address this issue, the
nanomorphology can be tuned by using the optimum donor and acceptor ratio so that efficient
percolation paths exist for the electrons and the holes and ȠCC is not significantly affected.
For P3HT:PCBM based solar cell this ratio is found to be 1:1 as per many investigations [19,
28].

Fig. 2.9: In bulk heterojunction devices since the D-A blends are spread over the bulk region the
charge carriers can dissociate over the entire region and thus BH cells have large active regions.

2.4.4 Tandem or Multi Junction Solar Cell

Tandem solar cells generally consist of two or more cells connected in a series
combination as shown in Fig. 2.7. This architecture tries to increase the absorption spectrum
range by use of different materials with different band gap. Such a structure is capable of

15
producing higher open circuit voltage and also higher current and thus can have higher
efficiency. However since the cells are series connected, if their currents are not matched
properly their efficiency falls severely.

Fig. 2.10 Simplified energy band diagram of a series-connected tandem bulk heterojunction solar cell
under open-circuit conditions when all electrodes provide an appropriate ohmic contact The subscripts
F, B, and T stand for front, back, and tandem respectively. [20]

2.4.5. Inverted Architecture

All the development in the cell architectures described above has been associated with
increase in efficiency of the OSCs. However as mentioned in introduction, stability has been
an important issue for these devices. Detailed description of all the factors leading to
degradation of organic solar cells has been reported by Jørgensen et al. [21]. One of the major
causes of the loss in efficiency is the degradation of the aluminium and the organic layer
interface [22]. This decay occurs due to reaction between the polymer and aluminium
electrode and also between aluminium and atmospheric oxygen. Besides this, the aluminium
electrode produced by vaccum evaporation has many micropores allowing for both oxygen
and moisture to diffuse though it and react with the polymers decreasing its efficiency [23].

16
 In order to solve these issues an inverted structure as shown in Fig. 2.11(b) is adopted
[7, 31]. The inverted architecture allows replacing the low work function Al metal with higher
work function metals like Au or Ag. High work function metals are more tolerant to
atmospheric oxygen and may also be fabricated using non vaccum based techniques like
lamination. It also replaces or avoids direct contact of acidic PEDOT:PSS layer with the
unstable ITO electrode [21, 24], generally, by using zinc oxide as anode. The PEDOT:PSS
layer and its details have been discussed later in Section 3.1.3.

The maximum theoretical open circuit voltage in any OSC is equal to the difference
between the LUMO of acceptor and HOMO of donor. For efficient capture and injection of
charges the work function of the electrodes should be as close as possible to these LUMO and
HOMO values. Since the higher work function electrodes like Ag align with the HOMO of
the donor as shown in Fig. 2.12 it is necessary to have the other electrode collect the electrons
from the LUMO of acceptor and act as anode. As this anode can be a TCO like ZnO
collecting electrons from the side of illumination this architecture is called inverted organic
solar cell compared to the architecture shown in Fig. 2.11(a) where holes are collected from
the side of illumination.

Fig. 2.11

(a) Normal geometry of a bulk-

heterojunction solar cell.

(b)
Inverted geometry causes electrons
and holes to exit the device in the
opposite direction. [25]

17
 These inverted device structures have shown efficiencies above 3% and more than one
year lifetime in external environment retaining 80% of their efficiency [24]. However,
eventually, even these devices degrade and the exact contribution of the various factors is not
well known - especially for inverted device architecture.

Fig. 2.12 Energy level diagram of different layers in an inverted organic solar cell. Use of inverted
architecture allows using higher work function metal without any adverse effect on the open circuit
voltage of the organic solar cell

18
Chapter 3

Non-inverted organic solar cells

Before studying the inverted architecture simple non inverted bulk heterojunction
organic solar cells were fabricated and characterized to optimize their fabrication process.

3.1 Experimental Details

The materials used and the main steps involved in the fabrication of bulk
heterojunction devices have been outlined below.

3.1.1 Substrate Preparation

Indium Tin Oxide (ITO) coated glass substrates (35 x 35 x 1.1 mm) with close to 85%
transmittance in the visible spectrum and sheet resistance of 15 Ω-cm were purchased from
Kintec Company. Lab measurements found the sheet resistance to be actually higher and

19
close to 20 Ω-cm. They were cleaned and prepared as described below before commencing
the fabrication.

i. The substrates were first ultrasonically cleaned in DI water to remove any dust
particles.
ii. Subsequently they were ultrasonicated in an acetone bath for 5 min to get rid of
any organic contamination and make the surface hydrophilic.
iii. The substrates were finally dried in an oven at 120 oC for 30 min to remove any
traces of moisture.

3.1.2 ITO Patterning

The ITO coated substrates were lithographically etched to obtain the pattern as shown in
Fig. 3.1 based on the following steps.

Fig. 3.1 Design of an offset printed mask used for ITO patterning

i. Positive photoresist (SPR-700 1:2) obtained from Microresist Technology GmBH

was spin coated on the substrate at 3000 rpm for 60 sec.
ii. The slides were then prebaked at 70oC for 15 min on a hot plate.
iii. Exposure to UV light was done for 10 sec through an appropriate shadow mask
similar to the Fig. 3.1
iv. Developer solution AZ400K in a developer to DI ratio of 1:4 was used to develop
the photoresist.

20
 v. Post baking was done for a period of 5 min at a temperature of 70 oC.
vi. The exposed ITO was etched by heating it in a solution of DI:HCl:HNO3 in the
ratio 15:4:1 at 60–65oC for 2 min. Checking with a multimeter showed the
exposed glass areas to be completely free of ITO.
vii. The etched samples were rinsed using DI water to remove the etchant remains.
viii. Finally any remaining photoresist was cleaned with acetone.

3.1.3 Application of PEDOT:PSS layer

While not essential for the operation of an organic solar cell, a PEDOT:PSS [poly(3,4-
ethylenedioxythiophene):poly(styrenesulfonate)] layer is coated on the substrate before
applying the active layer to improve the cell’s efficiency. It is a highly conducting organic
layer which allows efficient charge injection into the active layer due to close proximity of its
work function with the HOMO of P3HT. Application of PEDOT:PSS to the rough ITO layer
with irregular conductivity throughout the surface, allows both a uniform electrical
conductivity and mechanical smoothening leading to better growth of the P3HT film [26].
Described below are the main steps involved in its application.

i. Before application of PEDOT:PSS, the patterned substrates were RCA cleaned

by boiling in a 5:1:1 mixture of DI water, hydrogen peroxide and NH 4OH at
90oC for 20 min. Post RCA the substrates are thoroughly rinsed in DI water.
ii. PEDOT:PSS was diluted with DI water in the ratio of 1:2 and filtered with
0.45 micron filter (from Millipore) to remove any particulate matter.
iii. The filtered solution was spin coated on the substrates at 1000 rpm for 60s to
obtain a layer of c.a. 120 nm.
iv. The substrates were then heated in air at 120oC for 1 hour to obtain a dry film
of PEDOT:PSS on the substrate.

3.1.4 Active layer deposition

P3HT and PCBM were used as the donor and acceptor materials respectively in the
active layer blend. Regioregular P3HT was purchased from American Dyes whereas PCBM

21
was purchased from Nano-C, Inc. In order to prepare the active layer solution the
methodology adopted is as follows.

i. A solution of 10 mg of P3HT and PCBM each per ml of 1,2-dichlorobenzene,

was prepared by magnetic stirring for 12 hours at room temperature.
ii. This solution was filtered by 0.45 micron filter (from Millipore) to remove any
undissolved particles which may act as short paths in the solar cell.
iii. The active layer was spin coated on the PEDOT:PSS deposited substrates at
1000 rpm for 60 s to obtain a thin layer of approximately 80 nm.
iv. The active layer was then allowed to dry in 10 nbar vaccum for 20 min so as to
improve the crystallinity of the deposited P3HT [27].
v. Subsequently the layer was annealed at 90oC in vaccum for an hour. Although
the recommended temperature for annealing is 120 oC [27], the lower
temperature was used due to the machine’s limitation. Thermal annealing
increases crystallization of P3HT, improving its mobility [28] and
consequently efficiency of the fabricated devices. However excessive
annealing must be avoided since that may cause agglomeration of PCBM
molecules leading to a decrease in efficiency.

3.1.5 Metallization

After the active layer has sufficiently cooled to room temperature the anode was deposited by
thermal vaccum evaporation based on the following steps

i. A thick Al layer of approximately 1000 Ao was deposited on the substrate

perpendicular to the ITO layer as shown in Fig. 3.2. The intersection area of
5 mm x 5 mm defines the active area of the organic solar cell.
ii. The deposition rate is kept slow at the beginning to achieve good contacts and to
avoid any damage to the active layer and then slowly increased to keep the series
resistance low.

22
3.1.5 Encapsulation.

Since organic solar cells have low stability and easily degrade in the presence of
oxygen and moisture it is necessary to encapsulate them.

For encapsulation the regions of these substrates which define the active area were covered
with glass slides and the edges were sealed with commercial epoxy resin (FeviQuick). The
active layer material was then removed from the edges of the substrate using chloroform to
access the cathode contacts.

The completely fabricated solar cell is shown in Fig. 3.3 which consists of 4 cells numbered
from 1 to 4.

Fig. 3.2 Aluminium anode (Grey) and ITO cathode (black) regions defined on the Glass
substrates. The region of their cross section defines the active area and 4 such cells are
obtained per substrate.

Fig. 3.3 The fabricated ITO|PEDOT:PSS|P3HT:PCBM|Al layered bulk heterojunction organic solar
cell.

23
3.2 Characterisation and Discussion

The fabricated solar cells were characterized under an in house solar simulator using a
halogen lamp with output close to solar spectrum as the light source and a Parstat Potentistat
to plot the IV curves. The graph in Fig. 3.4 shows the J-V curve of the fabricated solar cells.

Dark
Light
1.4

1.2
Current Density (mA/cm )
2

1.0

0.8

0.6

0.4

0.2

0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6
-0.2

-0.4
Voltage (V)

Fig. 3.4. J-V Curves of fabricated organic solar cells in dark and under illumination.

The cells obtained show very good diode characteristics in dark with the knee voltage
close to 0.4 V. The equivalent circuit of a solar cell is shown in Fig. 3.5. The series resistance
(Rs) and shunt resistance (Rsh) are defined as the slope of the JV curve in open circuit and
short circuit conditions respectively. From the graph shown in Fig. 3.4 the series resistance of
the fabricated cells is calculated to be 250 Ω/cm2. The values obtained are two orders of
magnitude greater than published data [27] and could be one of the causes of low efficiency.
The shunt resistance is calculated to be 5.4 kΩ/cm2. The low shunt resistance obtained
explains the reduced Voc = 0.4 V which is 0.2 V less than the standard 0.6 V obtained for
P3HT:PCBM based devices [27]. Shunt paths directly formed from cathode to anode by each
component of the blend structure are reported to reduce Voc [30] and seem to be the case in

24
the present experiment. Although it has been shown that post-annealing i.e. annealing after
deposition of the Al layer can reduce these shorts and lead to an increase in both the shunt
resistance and open circuit voltage, devices without this process having Voc = 0.6 V have
been frequently reported in literature [27]. It is interesting to note that deposition and heating
of the active layer has almost always been done in vaccum or inert atmosphere when V oc =
0.6 V was achieved, unlike in this report and in Ref. [30].

Fig. 3.5. Equivalent circuit of an organic solar cell [29]. The series resistance (R s) represents the
combined resistance of the electrodes, the contact resistance and the resistivity of the organic material.
The shunt resistance represents the leakage current and thus the quality of the film. It decreases with
increasing light intensity. The current source represents the photovoltaic action of the solar cells
whereas the diode accounts for the diode like behaviour in dark which becomes very leaky under
illumination.

In spite of low efficiencies the fabricated solar cells had a fairly good fill factor of
0.52 mainly influenced by R s and Rsh representing its overall goodness as a diode. The
standard efficiency could not be calculated since the light source had not been completely
characterized yet however with a light intensity of 100 mW/cm2 the efficiency was around
0.06%.

25
Chapter 4

SILAR (Successive Ionic Layer Adsorption and

Reaction) deposition of ZnO

As described earlier, inverted morphology is the preferred architecture for stability. In

this morphology various other alternatives like CrOx and TiOx, can replace ZnO as anode,
each with their own advantages [31]. However, as far as commercial scalability is concerned
ZnO remains the best option available due to easy processing, environment friendliness and
low cost. It is a conducting oxide and films with required transparency needed for solar cells
can be fabricated. Also electron transfer from PCBM to ZnO is quite efficient [7] possibly due
to the proximity of the conduction band of ZnO to LUMO of PCBM at -4.1 eV. It has been
reported that loss in efficiency of OSCs also occurs due to degradation of ITO electrode by
acidic PEDOT:PSS [21] and that non ITO based solar cells have higher stability [32]. Thus
ZnO based solar cells lacking both ITO and PEDOT:PSS can further contribute to the stability
of OSCs. With a large exciton binding energy of 60 meV and wide band gap energy (Eg) of
3.37 eV at room temperature ZnO acts like a very good hole blocking layer [7] needed to
avoid charge recombination.

26
 The required ZnO layers can be produced in various ways like RF magnetron
sputtering, molecular beam epitaxy, spray pyrolysis, pulsed laser deposition, chemical vapour
transport (CVT) etc [33]. All these techniques are expensive and need some kind of extreme
environment. Hence the chemical route of ZnO deposition is very attractive. SILAR
(successive ionic layer adsorption and reaction) is one such inexpensive technique to produce
highly transparent ZnO films [34].

4.1 Background

The SILAR process, first described by Nikolau [35] is based on the adsorption and
reaction of cations and anions respectively on the substrate material from their precursor
solutions.

4.1.1 SILAR Deposition

Although SILAR processes vary quite a lot based on application and materials, it
basically consists of four general steps as described below and shown in Fig. 4.1.

i. Dipping of the substrate in cationic solution: The substrate material which

generally consists of glass needs to have an oxide layer present on its surface.
Such layers become negatively charged in water solutions above pH 2 [36] and
effectively attract the cations in a solution to form a thin adsorbed cationic layer on
the substrate material. This layer is covered with a charge balancing layer of
anions causing the formation of a double layer.
ii. Rinsing the substrate: The substrates are then rinsed in water to remove any
loosely adsorbed cation species. Both stirring [36] and ultrasonication have been
used for this purpose [37, 38].
iii. Dipping the substrate in anion solution: This causes the anions to diffuse
towards the adsorbed cationic layer. The reaction between these anions and the
adsorbed cations leads to formation of desired thin film layer.
iv. Rinsing the substrate again: This is done to remove any unreacted ionic species
from the substrate.

27
Fig. 4.1 Schematic view of thin film growth during one SILAR cycle. (a) cation adsorption cation
anion; (b) rinsing; (c) anion reaction anion cation and (d) rinsing. [39]

The above mentioned four step process can be repeated to achieve the required
thickness of the film. Many other factors like pH, temperature, concentration etc can affect the
growth rate of the thin film and have been described in detail elsewhere [39].

4.1.2 Advantages of SILAR

The main advantage of SILAR process is the lack of any kind of extreme
environment including vaccum. Since the process can be carried out in ambient conditions
SILAR equipments are simple and inexpensive to build. Also the process is environmentally
benign since it can be carried in a closed system allowing the chemicals to be recycled.
Compared with the relatively similar chemical bath deposition (CBD), SILAR has less loss of
material and increased control over the film thickness and quality by avoiding homogeneous
precipitation in the bulk reaction solution [40].

SILAR technique also allows controlling the roughness of the film which might help
to improve the device efficiency. It is also possible to dope the thin films deposited using
SILAR easily by adding the dopant reagent to the cationic solution. More than three orders of
magnitude improvement in conductivity have been achieved by such doping in ZnO films
[41]. This is important for OSCs where conductivity of the electrodes has an important
bearing on the efficiency of the solar cells. It has been shown that oxygen is important for

28
conductivity of ZnO films and hence the efficiency of cells with ZnO electrodes drop when
kept in an inert atmosphere or vaccum [42]. However, due to inherent intolerance of OSCs
towards oxygen it has to be avoided. This makes SILAR very attractive since it can be used to
make solution doped ZnO films which are insensitive to oxygen.

Inspite of all its advantages, SILAR still remains one of the relatively less studied
deposition methods. In the quest to make solar cells increasingly economical, SILAR can play
an important role in the fabrication of transparent ZnO electrodes. It was first used for
deposition of ZnO by Gonzailez [34] in 1995 who studied its transmittance, conductivity and
photoconductivity.

4.2 Experimental details

In the current report various methods for deposition of ZnO using SILAR were tried.
Since the main aim was to use them for fabrication of inverted organic solar cells, the work
was focused towards getting required transmittance and conductivity needed for organic solar
cells.

4.2.1 Preparation

Normal microscopic glass slides were used as substrate material for SILAR
deposition. The detailed steps involved in deposition are as described below.

i. The slides were first boiled in 20% H2SO4 for 30 min and then ultrasonically
rinsed in DI water.
ii. Afterwards they were ultrasonically cleaned in an acetone:ethanol (1:1) mixture
and allowed to dry in air. This treatment makes the substrates hydrophilic and
allows obtaining a more uniform film.
iii. A solution of ZnSO4.7H2O in ammonium hydroxide was used as the cationic
solution. Concentrated NH4OH (29%) was slowly added to 20 ml solution of
0.5 M of ZnSO4.7H2O till the solution becomes transparent.
iv. The solution was diluted with DI water to 0.1 M with a pH of 10.1 and was finally
used as the cationic solution.

29
 v. DI water maintained close to 95oC was used as the anionic solution.
vi. In order to achieve doping Al2SO4.16H2O was also added to the cationic solution
in some experiments corresponding to 1 and 2 at.wt. %.

4.2.2 Deposition

i. For deposition the slides were first dipped in the ZnSO 4 based cationic solution
for 5 sec.
ii. They were then sonicated in DI water for 10 sec.
iii. Subsequently they were dipped in the hot anionic solution of DI water at 95oC
leading to formation of ZnO.
iv. The slides were then rinsed in DI water for 10 sec again before continuing with
the next cycle.
v. After the deposition cycles the substrates were heated at 220oC for 15 min in
air to improve crystallinity and decompose any Zn(OH)2 present.

Besides the process mentioned above (referred to as L0) three more dipping periods
were experimented. First one (L1) was exactly similar to L0 other than that rinsing was not
assisted by sonication. Second one (L2) consisted of 10, 20, 12 and 15 sec for ZnSO4 dip, DI
water rinse, Hot DI water dip and DI water rinse respectively and was based on Ref [43]. The
third method (L3) consisted of 15, 20, 30 and 20 sec for ZnSO4 dip, DI water rinse, DI water
sonication and hot DI water respectively and was based on work done by Gao et al. [37]. Both
L2 and L3 methods had 63 mg Al2(SO4)3.16H2O added to the cationic solution corresponding
to 2 at.wt.% doping with Al.

4.2.3 Measurements

The film thickness was measured by Ambios XP-Plus 100 stylus type profilometer
using a stylus pressure of 2 mg. Dilute H2SO4 was used to etch the deposited films along the
edges of the slides and the thickness was measured with respect to the etched surfaces. The
films were scanned at multiple locations and the average value of the thickness was used for
calculations.

30
 The structural and morphological characterization of as-deposited layers were studied
by 45 kV Philips X’pert Multipurpose X-ray Diffraction System (Cu Kα radiation) and
scanning electron microscope (SEM) (Raith-GmBH). A LAMBDA 950UV/Vis
spectrophotometer from Perkin Elmer was used to measure the transmittance in the frequency
range from 200 to 800nm. The total transmittance was measured using the integrating sphere
accessory of the spectrophotometer. The conductivity of the films was measured using
Ecopia’s HMS-3000 Hall Measurement System. Contacts were made at the edges of square
cut glass slides (1cm X 1cm) by soldering with InSn alloy. All measurements were done in
dark to avoid any effect of photoconductivity.

4.3 Results and discussion

Addition of ammonium hydroxide to ZnSO4 solution causes a white precipitate of zinc

hydroxide Zn(OH)2 to appears according to the following reaction [44].

ZnSO4 + 2NH4OH Zn(OH)2 + (NH4)2SO4

However, on further addition of ammonia, the precipitate was dissolved forming (NH4)2ZnO2
as per the following the reaction

Zn(OH)2 + 2NH4OH (NH4)2ZnO2 + 2H2O

Thus the overall reaction leading to the formation of ammonium zincate is given by

ZnSO4+4NH4OH (NH4)2ZnO2 + (NH4)2SO4+2H2O

It has been found that zinc hydroxide dissolves in ammonium hydroxide because of
the formation of tetraamminezinc hydroxide Zn(NH3)4(OH)2 [45]. Its ion, the
tetraamminezinc complex [Zn(NH3)4]2+ is absorbed on to the glass substrate and is the key
element in SILAR deposition. Gao et al.[23] has suggested that the Zn(NH 3)42+ reacts with
hot water to deposit a heterogeneous solid film of Zn(OH) 2 on the substrate which reacts at
temperatures exceeding 50oC to from ZnO.

In order to have a good quality uniform film it is necessary to have a hydrophilic

substrate surface which would allow the cationic solution to uniformly cover it. Boiling in hot
dilute sulphuric acid is a simple method to increase hydrophilicity of the substrate. The
silicate glass consists of a random three-dimensional network of [SiO4]4− tetrahedra, however,

31
at the surface, the continuous Si-O-Si structure of SiO2 can be interrupted by silanol group
Si-OH. It is speculated that there is an increase of the Si-OH group and formation of SiO2 rich
layer on the surface of the glass substrate when dipped in dilute acid due to exchange of alkali
in the glass with hydrogen ions in water. This is thought as being responsible for the
hydrophilic property of glass substrate after the treatment in hot dilute sulphuric acid solution
[37]. Sonication in acetone and ethanol mixture is also supposed to enhance hydrophilicity as
well as to remove any impurity.

It has been shown earlier that ZnSO4 concentration close to 0.1 M is the best for film
growth [41, 44]. Consistent with the literature good films were obtained for this
concentration. When tried with a concentration of 0.5 M ZnSO4 solution, white powdery
patches were obtained on the surface and hence all experiments were carried at 0.1 M
concentration only. The DI water used for rinsing after as the second step was replaced after
every 6 cycles and was shown to give better films by visual inspection. While it is well known
that pH is an important parameter for SILAR, Mitra et al. [44] has mentioned a pH between
11 and 11.1 to be critical for good film growth. Gao [44] and Vargas [46] on the other hand
has emphasized more on the importance of Zn:NH 3 ratio and recommended it to be 1:10. For
the processes carried out in this report it was possible to deposit good quality films at the
recommended Zn:NH3 molar ratio of 1:10 even at a lower pH of 10.1.

4.3.1 Thickness measurements

Fig. 4.2 shows the average film growth rate for the different SILAR variations. It has
been calculated by dividing the total film thickness by the number of deposition cycles.
Addition of Al2(SO4)3 to the solution does not seem to have any distinct effect on the growth
of the film as both L0 with 2 % Al2(SO4)3 and L0-undoped have same growth rate, close to 20
nm/cycle. This growth rate for 0.1M cationic solution is comparatively higher than those
quoted in literature [44, 47] and most probably is the effect of smaller pH of the cationic
solution. On every subsequent re-entry of the slides in the cationic solution, a part of the film
is dissolved back into it. This helps to increase the quality of the film but also decreases the
growth rate. Hence at a pH of 10.1 the films seemed to grow comparatively faster. The key to
obtaining good quality films at lower pH could be ultrasonication which effectively removes
any weakly bound micro crystals allowing better nucleation of the ZnO film.

32
 70
64

60
50

Growth Rate (nm/cycle)

50

40

30 26
20 20
20

10

0
L0-(0%) L0-(2%) L1-(2%) L2-(2%) L3-(2%)

Fig. 4.2 The average growth for different SILAR process. The values in the bracket signify the amount
of Al2(SO4)3.16H2O added to the cationic solution in at.wt. % doping of Al.

Both L2 and L3 show increased growth rate, L2 being greater by 14 nm/cycle. The
increase in growth rate for these processes was an expected phenomenon because of the
increased dipping periods. The main reason for experimenting with the increased time period
was the expected increase in conductivity [43] which is described in the Hall Effect
measurement section. There are two main differences between L2 and L3. One, L2 has
smaller dipping period both in cationic and in anionic solution as described earlier. Second in
L2 both oxidation of Zn ions to Zn(OH) 2 and sonication is done in the same step where as in
case of L3 the second step is exclusively used for oxidation of Zn ions. In spite of this L2
shows a faster growth rate which means that sonication has a strong tendency to lower the
growth rate by removing the loosely bound ions.

4.3.2 XRD Analysis

Fig. 4.3 shows the XRD pattern of the films deposited by the various processes. All
the films obtained were of polycrystalline nature with a hexagonal wurtzite crystal structure

33
as confirmed by their XRD patterns which is in conformance with JCPDS 036-1451 card for
ZnO [48]. It can be seen that these films have a strong c axis orientation perpendicular to the
substrate with (002) peak having the highest intensity among the three main peaks. Similar
results have been reported earlier in literature [34, 41]. The other peaks shown in Fig. 4.3 are
obtained at (100) and (101) planes.

Fig. 4.3 XRD patterns of films deposited using (a) L0–25 cycles , (b) L0–25 cycles annealed, (c) L0-
50 cycles annealed, (d) L1-50 cycles and (e) L1-50 cycles annealed. All made from solutions
impurified with Al2(SO4)3 corresponding to 1% doping.

Increasing the number of deposition cycles from 25 to 50 clearly increases the

crystalline nature of the film as well as the c-axis orientation. The peaks corresponding to
(100) and (101) start becoming more visible and the peak corresponding to (002) increases
further. Annealing at 220oC for 15 min further improves the crystallization with the (110)
peak showing up more prominently. However, this leads to a decrease in the preferential

34
orientation of the films. Similar results were reported in Ref. [49] where a trend towards
randomization of crystallites was observed after the heat treatment in air at 350 °C. It is
believed that absence of the lateral restriction in the porous ZnO structure obtained by SILAR
may cause the growth of crystallite along (1 0 0) plane and decrease in the c-axis orientation.
However, the underlying mechanism for this change in orientation caused by annealing is still
not clear [37].

Also film deposited with sonication assistance have more visible (100) and (101)
peaks as compared to the unsonicated ones. This is most probably due to increase in
crystallinity of the films as claimed by Gao et al. [37, 38]. Another prominent change on
annealing the sample is the removal of peak at 2θ = 9.7 o which is speculated to belong to
Zn(OH)2 and removed after annealing. However no crystallite structure of Zn(OH) 2 could be
matched to that peak. Instead that peak matches with zinc oxide sulphide which might be
present in the sample due to the zinc sulphate used for the original deposition.

The crystallite grain size in the deposited ZnO films have be calculated based on the
broadening of the XRD peak.

By Sherrer equation, the crystallite grain size is given by the formula

D = kλ/βcosθ.

where,

D is the grain size

K is the Scherrer constant

β is the integral breadth of peak (in radians 2θ) located at angle θ and

λ = wavelength of radiation

For the (002) peak (β = 0.19o, 2θ = 34.41o and k = 0.94) the crystalline grain of this film is
about 45 nm in size. This has been verified later by the SEM analysis.

35
4.3.3 SEM and Optical images

The films obtained using SILAR have good density over the surface as seen in Fig.
4.4 which is a 100x optical image. The clean portion in Fig. 4.4 is the area from which ZnO is
etched. Fig. 4.5 and Fig. 4.6 shows the low and magnified SEM images for films obtained
with L0 (sonication assisted) and L1 (non-sonicated) processes respectively. In spite of the
good density and coverage, the obtained films are porous and do not completely cover the
surface as seen in the SEM images at sub micrometer scale.

The ZnO films obtained are in the form of interconnected spheres of approximately 50
nm diameter as shown in the Fig. 4.5 (b). These values for the crystallite size obtained are
also verified by the XRD analysis which show a grain size of 45 nm based on Scherrer
equation. While sonication assisted films are better interleaved, films obtained otherwise
seem more like islands of ZnO crystals. These films have a flake like structure with much
reduced density of the spherical nano crystals. Compared to L0 based slides the unsonicated
films have a smooth XRD background. It is speculated that sonication leads to formation of
many crystalline nano clusters with different orientations in the ZnO films causing the rough
XRD pattern.

Fig. 4.4 Optical image (100X) of ZnO deposited using L0 process on glass substrates. ZnO is etched
from the clean area using mild H2SO4

36
 (a)

(b)

Fig. 4.5. Low (a) and Magnified (b) SEM images of ZnO films deposited using sonication assisted L0
process after 50 deposition cycles. The crystallites of sizes 50 to 60 nm can be easily seen in the
magnified image.

37
 (a)

(b)

Fig. 4.6. Low (a) and Magnified (b) SEM images of ZnO films deposited using L1 process without use
of sonication after 50 deposition cycles. Far less density of spherical crystallites is observed and their
size is also smaller.

38
4.4.4 Spectrophotometry

All the films obtained had a total transmittance (Td) close to 90% in the visible and in
the near UV region as shown in Fig. 4.7. Increase in film thickness from 400nm to 1um with
increased number of deposition cycles has very little effect on the total transmittance;
however, this greatly affects the normal transmission (Tn). It can be ascribed to the increase in
roughness of the film with increasing number of cycles most probably due to the increase in
crystallinity as can be derived from the XRD. Clearly the effect is not due to increased
absorption due to increasing thickness. Any distinct change in the transmission pattern of ZnO
films due to addition of Al2(SO4)3 in the solution was not observed.

90

80
Transmittance (%)

70

60

50

40

30

20
50 cycles - normal
10 25 cycles - normal
0
50 cycles - total
25 cycles - total
-10
200 300 400 500 600 700 800

Wavelength (nm)

Fig. 4.7 Total and Normal transmission pattern of deposited ZnO films with 25 and 50 cycles

Optical haze factor of the films at a particular wavelength were calculated using the
equation.
[(Td - Tn)/ Td] x 100
The 25 cycle deposition showed a smaller haze factor of 52.1% whereas the 50 cycle
deposition process showed a haze factor of 83.3% at 500 nm consistent with the theory of
increasing roughness. The haze factor which is a measure of the diffusion of light is an

39
important parameter for transparent films used in photovoltaics. Increased diffusion of
sunlight with haze assists in better capture of photons by a solar cell increasing its efficiency.

4.4.5 Hall Effect measurements

Based on private communication with Lupan [43] it was learned that increasing
deposition period led to increased conductivity for films deposited as described in [41]. As a
result L2 and L3 cycles with increased deposition time period were experimented. Fig. 4.8
and Fig. 4.9 shows the bulk concentration, mobility and sheet resistance values obtained for
the films deposited by the different variations of SILAR and for different doping
concentrations measured using Hall-effect. Measurements showed n-type conductivity for the
deposited ZnO films.

From Fig. 4.8 and Fig. 4.9 the mobility seems to increase with both the use of
sonication and annealing except for L2 where it has decreased. The increased mobility
corresponds to increased crystallinity of the film. As speculated by Gao in Ref. [38]
ultrasonication might lead to breakdown of NH3 and produce free H* radicals which can
promote the transformation of Zn(OH) 2 to ZnO and thus improve the crystallinity of ZnO
particles. Besides this, the mere act of good mechanical removal of loosely bound ions on the
substrate can contribute to the growth of a homogenous film. Increased mobility of films
prepared using ultrasonication method strengthens the hypothesis of increased crystallinity in
such films. Although any significant increase in conductivity was not achieved by increased
deposition cycles L3 still was able to get the best mobility and resistivity value as seen in
Fig. 4.8(b) and 4.8(c) respectively.

Annealing also contributes to the decrease in resistivity of the ZnO films. This
decrease in resistivity occurs due to increased mobility which most probably is caused by the
reduction in the grain boundary region which is integrated into the crystallite during the
annealing process [50]. Mobility of the order of 102 cm2/Vs was realized in the deposited
films and the obtained resistivity was of the order of 10 5 Ω-cm.

40
 1E+12

Carrier Conc / cm3

1E+10
1E+08
1E+06
1E+04
1E+02
1E+00
L0 (A) L1 (A) L2 (A) L2 L3 (A) L3

(a)

1E+03
Mobility (cm2/V-s)

1E+02

1E+01

1E+00
L0 (A) L1 (A) L2 (A) L2 L3 (A) L3

(b)

1E+06
Resistivity (Ω-cm)

1E+05
1E+04
1E+03
1E+02
1E+01
1E+00
L0 (A) L1 (A) L2 (A) L2 L3 (A) L3

(c)

Fig. 4.8 Comparision of (a) carrier concentration, (b) mobility and (c) resisitivity of ZnO
films obtained by different SILAR process. A in the braces represents annealing in air at
220oC for 15 min.

41
 1E+12

Carrier Conc / cm3

1E+10
1E+08
1E+06
1E+04
1E+02
1E+00
Undoped Undoped A Doped 1% A Doped 2% A

(a)

1E+03
Mobility (cm2/V-s)

1E+02

1E+01

1E+00
Undoped Undoped A Doped 1% A Doped 2% A

(b)

1E+06
1E+05
Resistivity (Ω-cm)

1E+04
1E+03
1E+02
1E+01
1E+00
Undoped Undoped A Doped 1% A Doped 2% A

(c)

Fig. 4.9 Comparision of (a) carrier concentration, (b) mobility and (c) resisitivity of ZnO
films obtained by different doping concentration in L0 SILAR process. A represents
annealing in air at 220oC for 15 min.

42
 It can be seen that the bulk concentration remains quite constant and close to 1011
carriers/cm3 among the various process. It appears to increase by an order for films formed
without sonication however such films show poor mobility compared to the other process.
Since no significant increase can be seen in the charge carrier concentration even after doping
up to 2 at.wt.% with Al2(SO4)3 it is believed that Al is not incorporated into the ZnO
crystallite. Along with the resistivity measurements neither of the analysis described earlier
show any significant changes in the properties of the films impurified with addition of
Al2(SO4)3 . This most probably is due to lack of Al incorporation. Several papers [41, 47]
claim resistivity as low as 100Ω-cm obtained by doping with only 1 at.wt.% Al when NaOH
was used as the base instead of NH4OH. However to the best of the author’s knowledge no
work has been done on doping ZnO deposited by NH4OH based SILAR, especially using
Al2(SO4)3 as the dopant salt.

It has been shown earlier by Ristov et al. [51] that ammonium zincate is the best
among the different zinc complexes studied by him and that films formed using ammonium
zincate have higher transparency compared to the others. Also Mitra and Khan [44] claimed
that trace amount of Na was present in ZnO films synthesised using NaOH which may make
the films unsuitable for any ultimate use, more so for the case of an already unstable organic
solar cell, hence ammonium zincate was chosen as the ideal candidate for the current
deposition. However it seems that in the reported conditions doping of Al cannot be as easily
achieved as with NaOH. It is worthwhile to note that Al2(SO4)3 cannot be readily dissolved in
the cationic solution at a pH of 10.1 with ammonia already added to it. The Al2(SO4)3 needs to
be dissolved first in the 0.5 M ZnSO4 solution and then NH4OH is slowly added leading first
to zinc hydroxide and aluminium hydroxide precipitation and then its subsequent dissolution
on addition of excess amount of NH4OH. It is speculated that gelatinous Al2(OH)6
precipitated due to addition of NH4OH in spite of not being visible in the solution, is not
dissolved back due to its low solubility in ammonium hydroxide. Lack of Al ions in the
solution due to this could have been the reason for non incorporation of dopant Al atoms in
ZnO films and thus no effect on charge carrier concentration.

All electrical characterisations were done in dark. However it should be noted that
ZnO exhibits photoconductivity and much lower values for resistivity would be obtained if
these reading were taken in AM 1.5 conditions. SILAR deposited ZnO films have shown dark
to light current ratios of the order of 106 under 900 W/m2 of illumination. [34].

43
Chapter 5

Conclusion and Future Work

It was attempted to fabricate non-inverted organic solar cells and optimise their
fabrication process. Successive ionic layer adsorption and reaction (SILAR) process was
studied as a method to deposit ZnO required for fabrication of inverted organic solar cells
know to show better stability. The main conclusions based on this work can be summed up as
follows.

5.1 Conclusions

5.1.1 SILAR

1. High transmittivity ZnO films with total transmittance close to 90% in visible and near
UV region have been deposited using SILAR.

44
 2. The deposited films have wurtzite structure and a strong c-axis orientation. They are
porous and consist of spherical nano crystals with grain size close to 50 nm.
3. Increasing deposition period in the cationic solution lead to a faster film growth rate.
Compared to similar studies reduced pH also led higher growth rate of the films.
4. The surface roughness and consequently the haze factor of the films increased with
increasing deposition cycles. Haze factor above 80% was achieved at 500 nm making
SILAR an excellent method to deposit light diffusing electrodes not only for organic
solar cells but inorganic ones as well.
5. Crystallinity of the deposited films improved on increasing the number of deposition
cycles from 25 to 50. There was also an increase in c axis orientation.
6. Crystallinity and thus the mobility of ZnO films increase by annealing the films in air.
This allows them to show lower overall resistivity although there is a loss of
orientation after annealing.
7. Use of sonication while rinsing seems to increase the crystallinity of the films and thus
contribute to increased conductivity.
8. Al2(SO4)3 cannot be effectively used as a dopant for NH4OH based SILAR deposited
ZnO at least for concentrations up to 2 at.wt.%. However sonication assisted SILAR
can be used to deposit annealed ZnO layers with resistivity less than 10 5 Ω-cm.

5.1.2 Non-Inverted OSC

Non inverted solar cells with efficiency close to 0.06% were fabricated. In spite of their low
efficiency a good fill factor of 0.52 was obtained for the cells.

5.2 Future work

It has been already shown that required transmittance can be obtained in SILAR deposited
ZnO layers. However since required conductivity was not achieved after doping with
Al2(SO4)3 in 2 at.wt.%, higher concentrations of doping can be studied. Incorporation of Al
into the films needed to be verified using techniques like EDX (Energy Dispersion X-ray
Spectrometer). If ZnO thin films of required conductivity can be synthesized they can be used
to fabricate inverted organic solar cell and its performance can be evaluated.

45
 Post thermal annealing can be tried on the fabricated organic solar cells to study
improvement in their performance. The annealing of the active layer can also be carried at
higher temperature and attempts can be made to improve R s and Rsh.

46
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51
Acknowledgements

I would like to express my utmost gratitude to my guide Prof. M. Neergat for his
invaluable guidance and support and believing in me all the time.

I would like to thank the Electrical Department for providing me with the required
infrastructure and equipments. Part of the work reported in this thesis was carried out at the
Center of Excellence in Nanoelectronics (CEN) of the Department of Information Technology
at IIT Bombay. This work could not have been completed without the help of many from
CEN especially Ramesh N, Anjum, Neha, Sheetal, Jayshree Maam, Mani Maam, Vanita, Tari
Uncle, Pradeep, Rajendra, Rajesh, Nabanita, Abhishek, Sunil, Mrinmoy, Gayatri and the list
goes on. My heartfelt thanks to all of them for going out of their way to help me.

I am thankful to Prof. Aslam, Prof. Major, Anshuman and Devendra from Physics
Dept for the transmittivity measurements. The Hall Effect measurements were done thanks to
access provided by Prof. Dusane and help of Vishal Khetan from MEMS. My discussions
with Mr. Rajkumar from MEMS for XRD analysis were very helpful.

I would also like to thank Prof. SSK Iyer and his team from IIT Kanpur especially
Arun Tej and A. Dembla for giving me an opportunity to have hands on experience on actual
fabrication of Organic Solar Cells and Prabhu Goel Foundation for funding my stay in IITK.

Last and most important I would also like to thank both my extended family,
Department of Energy Sci. & Engg. (DESE) including Urja lab staff as well as my own
family for giving me all the support whenever needed. DESE has the best office staff in entire
IIT Bombay. Thank You!

52