08 Chapter 2

CHAPTER 2
Proof of concept: Upon photo illumination of a dye sensitized solar

cell (DSSC), electrical energy can be stored directly to a capacitor
which is integrated to the dye sensitized solar cell
2.1. Introduction
Conventionally solar cells are used in conjunction with battery systems to
effectively utilize them as reliable sources of power. The need for an additional
storage system raises the overall cost per kWh of the power source. Recently,
new approaches have been investigated whereby separate battery systems may be
avoided or at least partially replaced. One such approach has been the introduction
of thin film photo-charged capacitors [1-4]. This device consists of a capacitor
that can be charged by electrons (converted from photons) from the solar source.
This approach helped in the development of a module “Photocapacitor” which
directly feeds electricity to the capacitor upon photo generation and energy gets
stored in it. The light-driven capacitor consists of a DSSC as the light absorbing -
generation part and activated carbon layer as the storage part. This reported article
[1] shows photo charging upon illumination and discharging. Charging current
(photocurrent) in the photocapacitor is fully dependent on the intensity of the light
and decreases with time until charging gets saturated discharging is studied by
applying a constant discharging current. The working of cell is as follows,
Lithium iodide ( LiI) in the TiO2 mesoporous structure is the electrolyte,
which react with the photo-induced holes of the dye as a hole trapping agent to
regenerate the dye (This mechanism of regeration is clearly explained in a recently
published paper by Gerrit et al [5].
Dye (hole) + LiI Dye + Li+ + (1/2)I2

Proof of concept: Upon photogeneration ….
The resulted I2, can simultaneously react with activated carbon layer
(Figure 2.1) and get reduces to regenerate LiI. It is known that both I- and I2
strongly interact with activated carbon by adsorbing on its microporous surface.
After charge separation, electrons flow via external circuit to activated carbon
layer of the counter electrode. Photo-generated holes of the dye move to the
activated carbon layer of photoelectrode. Holes and electrons are ultimately
accumulated on the microporous surface of activated carbon that holds the electric
double layer in contact with a liquid electrolyte of high ionic concentration.
Figure 2.1: Two-electrode sandwich type structure of the carbon incorporated

photocapacitor (upper) and charge-transfer mechanism in the processes of photo-
charging and discharging (lower) [6].
Amrita Centre for Nanosciences and Molecular Medicine 31

The illuminated cell develops a negative photovoltage, which is the

driving force for self-charging reaction. When a constant discharging current is
applied by an external current source, the cell voltage exhibited a constant
decrease with time, an initial IR drop due to the cell resistance. This linear
decrease of voltage is a characteristic of the double-layer capacitor [7].
Photocapacitor achieves simultaneous conversion and storage of light energy
exhibiting an open-circuit voltage >0.45 V, a charge capacity per area of 354 mC
cm-2 and capacitance of 0.69 Fcm-2. The charging voltage is 0.45 V which is lower
than the maximal open circuit voltage of DSSC (~0.8 V). This is apparently
influenced by the presence of a space charge Schottky barrier at TiO2, which is
developed when a metal-Ti plate and semiconductor layer comes in contact, which
prevents charge flow from the metal to the semiconductor. To overcome this,
another [3] designed a three-electrode type photocapacitor, in which an internal
electrode is inserted between photo and counter electrodes (Figure 2.2), which
functions on its both sides as the cathode of photoelectrode and the anode of
capacitor. The device showed excellent cycleability for repeated photo-charge and
discharge, corroborating high stability of the carbon-based electrochemical cell.
Even though it stores energy, the main observed disadvantages are:
 Independent working as a solar cell and a capacitor is not

practically possible, i.e., once the capacitor is fully charged the
solar part wouldn’t convert light to electricity and for the further
storage energy stored should be utilized.
 The workflow leads to an incomplete operation of the Gratzel
photo-electrochemical (or dye sensitized solar) cell and hence
lower storage efficiency.
 The activated carbon used for the photocapacitor is micro porous
and hence limited in available surface area for charge storage.
 Once the photo-capacitor is fully charged further light exposure is
not converted into energy, the capacitor has to be drained for the
incremental energy storage.

Figure 2.2: Schematic diagrams of 2-electrode phtocapacitor and 3-electrode

photo capacitor [6]. Three-electrode type photocapacitor is an improved version of
the basic two-electrode type by introducing an internal bi-functional electrode
working as cathode of the photovoltaic cell and anode of the storage cell,
achieving high charging voltage.
Another study reported by Hiroki Nagai et al [8], in which a three-
electrode “Solar rechargeable battery” type energy storable dye sensitized solar
cell was constructed with DSSC as the photon to electron generator and
conducting polymer as charge storage electrode material. Gratzel’s cell in front-
side illumination mode and pyrrole electro-polymerized on ITO to get polypyrrole
film were taken as the photovoltaic unit and charge-storage electrode respectively;
this system showed an efficient photo charging by visible light irradiation. But
detailed characterization like photo charging and discharging is not carried out in
this study.
In our work we have introduced a novel approach for the development of
an integrated module that consists of both a dye sensitized solar cell and a storage
capacitor, both of which are capable of independent functioning as well as in an
integrated manner. In other words, power can be drawn from the solar cell during
solar exposure, or when the solar exposure is absent, power can be drawn from the
capacitor. Thus, the output load would not be dependent on the continuous
presence of solar radiation and the device can work uninterrupted during the

presence or absence of light. Because of its independency this integrated structure

also enables the integration of other storage units like super capacitors, batteries
according to the needed power and energy density. This initial study explores the
scientific basis of such an integration using, as an example, a cost effective [9-15]
dye sensitized solar cell and a dielectric capacitor as the storage device. The
principles of integration explained below are not dependent on the choice of the
type of solar cell or storage device selected, but it shows the preliminary results,
which can form the basis of the development of a solar panel that stores
electricity in it.
Different modes of Illumination on DSSC
Two possible modes of Illumination on Dye sensitized solar cells are
(a) Front side illuminated DSSC
(b) Back side illuminated DSSC
In both the modes, DSSC can be integrated with a storage unit. Figure 2.3(a)
shows the schematic of front side illuminated DSSC with a simple storage unit.
The integration of DSSC and capacitor is not inbuilt but it is through an external
contact whereas for back side mode there is a common electrode which provides
an inherent integration. Initial experiments were carried out with front side
illuminated DSSC with storage unit but satisfactory result couldn’t be obtained
due to higher self discharge.
In front side illumination capacitor is connected at the counter electrode
side. The other side of the counter electrode is coated with platinum and carbon
nanotube is coated on this side and device is assembled as front side illuminated
cell with CNT symmetric capacitor as shown in figure 2.3(b).
Upon illumination the voltage across the capacitor starts to increase slowly
and it reached up to 0.65 V in 250 seconds, but it was found that almost 90%
voltage decays when illumination turned off. This discharge is not forced by the
application of an external current unlike in back illuminated scheme. This self
discharge is an undesirable property; this could be due to the improper external
contact between DSSC and capacitor and also due to the non continuous interface.

Figure 2.3: (a) Schematic illustration of front side illuminated DSSC with
capacitor. (b) Voltage variation integrated cell upon photo illumination and self
discharge from the capacitor when light turned off.
The DSSC is integrated to capacitor by an external contact, which is

merely a physical contact but not an inherent integration. Hence this study was not
pursued and experiments were done with back side illuminated cell as generator
where inherent integration is through a common titanium plate (Figure 2.5).
2.2. Dye sensitized solar cell
A dye sensitized solar cell is a photo electrochemical cell in which dye
molecules are sensitized on wide band gap semiconductors like ZnO, TiO2, SnO2
[16-19] which separates electrons from the photo-excited dye molecules. The
figure (Figure 2.4) shows the working principle of DSSC: the photons incident on
the cell are absorbed by the dye molecule and an electron from the molecular
ground state (S0) gets excited to higher level (S*) and this excited electrons are
injected into the conduction band of the wide band gap semiconductor leaving dye
molecule in an oxidized state (S+). The injected electron gets transported through
the semiconductor to the transparent conducting oxide (TCO) over which the
semiconductor nanoparticles are coated and finally through the external load to
the counter electrode. At counter electrode electron gets transferred to electrolyte
(Iodide/Tri-iodide couple) by the reaction and finally oxidised dye gets reduced by
iodide in the electrolyte.
I3- + 2e- 3I – [at electrolyte/counter electrode interface] ------- (2.1)
3I – I3- + 2e- [at dye/electrolyte interface] ------------ (2.2)

Further, a counter-electrode material of ample catalytic activity becomes

necessary for ejecting electron to iodine, platinum is usually used for this purpose,
which simultaneously acts as catalyst and electron conductor.
The fill factor and efficiency of DSSC is given as:
ff  Vm * I m  Voc * I sc  -------------------------------------- (2.3)
Efficiency ( )  Voc * Isc * ff  ----------------------------------- (2.4)

I
Where Vm and Im are the maximum voltage and current, Voc is the open circuit
voltage Isc is the short circuit current and I denotes the intensity of solar radiation
which is 100mW/cm2.
Figure 2.4: Schematic diagram of DSSC.
The nanoparticle or nanotubular wide band gap semiconducting materials

provide higher surface area for the absorption of dye molecule on the electrode.
Nano-tubular arrays not only provides high surface area but also eliminates inter
grain boundaries, facilitates ballistic charge transport [20-21] have studied effects
of grain morphology and electron trapping on the transient response of

photoelectrons moving through the TiO2 grains in a dye-sensitized nanocrystalline

solar cell using a multi-time-scale random walk Monte Carlo model. This
approach enables to simulate transport for electrons moving through spherical
connected grains in a three dimensional (3D) voided network and the effect of the
size of inter-particle boundaries on carrier dynamics. The time taken for the
transport are long (around 0.1 ms) because of deep traps in the TiO2 grains. The
nanoparticular based DSSC has very recently achieved maximum efficiency of
12.3 % [22] and the maximum reported efficiency with TiO2 nanotube DSSC is
7.3% [23]. In nanoparticular DSSC, TiO2 nanoparticles were coated on a
transparent conducting oxide coated glass substrate which facilitates front side
illumination whereas in TiO2 nanotubular based DSSC, TiO2 nanotubes were
grown on an opaque Ti substrate. The practical difficulty for growing very long
and well ordered TiO2 nanotube on a transparent substrate is the main reason for
the low efficiency also some effort were made to grow TiO2 nanotube on TCO
substrate [24]. The preferred mode of illumination for DSSC is front side (Light
through dye coated working electrode) so that maximum photon gets absorbed by
the dye molecule, but in back side illumination mode (light from the counter
electrode), a part of photon get reflected by platinum coating on counter electrode,
some gets absorbed by the electrolyte and only remaining portion of photons
interact with dye molecule. In this study, we have progressively evolved a novel
DSSC-supercapacitor integrated structure [25], which includes nano-structured
DSSC and different forms of supercapacitor structures having different energy and
power density. This stores energy simultaneously and efficiently upon photo
generation, and enables material level implementation of the dual functions of
electricity generation and storage. A direct storage thin film cell enables the
incorporation of a thin photocell (DSSC) capable of electrical generation and
integrating it with a storage cell minimizing circuitry and diminishing the
electrical losses due to circuitry. The device is capable of repeated photo-charge
and discharge. A merit of this device is that both generation and storage part is
capable of functioning independently so that photovoltaic unit and storage units
can be independently optimized by changing the materials to maximize the
performance. The Gratzel cell is completely operational thus maximizing
generation and storage efficiencies.

2.3. Integration of DSSC with a dielectric capacitor

Integration scheme is shown in Figure 2.5 which is basically a DSSC
coupled with ZrO2 dielectric capacitor. In Integration, the heart of the integration
is a TiO2-Ti-TiO2 double anodized layered structure (DALS) (Figure 2.5) which
separates the photovoltaic (PV) component from the storage component of the
integrated device. On one side of the DALS the device contains the dye and
electrolyte and counter electrode of the PV component. Independence of the solar
cell is maintained because the TiO2-Ti layer of the DALS acts as the primary
electrode or as the working electrode of the PV. On the other side of the DALS is
a solid-state Zirconia dielectric layer to act as a capacitor component followed by
a single side anodized layered structure (SALS) (TiO2-Ti). The DALS acts as
independent electrodes for both the PV and the capacitor while the SALS act as
the electrode for the capacitor.
2.4. Advantages of Integrated structure
 Both DSSC and Storage units are capable of independent functioning as
well as in an integrated manner (Figure 2.5(c)).
 Power can be drawn from the solar cell during solar exposure, or when the
solar exposure is absent, power can be drawn from the capacitor.
 Because of its independency this integrated structure enables the
integration of other storage units like super capacitors, batteries according
to the needed power and energy density.
 This integrated structure enables the integration of any types of solar cell
units like thin film, silicon, DSSC etc, according to the need.
 Gratzel cycle is complete.
 Nanomaterials like nanotubes form heart of both PV and storage structure.

Platinum coated
ITO
Dye coated TiO2
Electrolyte nanotube
Solar O/P
DALS
ZrO2
Capacitor O/P
SALS
Ti plate
TiO2 nanotube
Figure 2.5: (a), (b) Schematic representation of integrated structure of DSSC with
ZrO2 dielectric capacitor (c) Different schemes of integrated structure (i) solar cell
scheme (ii) capacitor scheme (iii) integrated scheme.

The charge workflow in the integrated cell can be briefly explained as

follows: illumination on the solar cell generates electrons, which are injected into
the first TiO2 semiconducting layer of the DALS and flow along the nanotube
length to the common Ti plate of the DALS. From here, provided the voltage is
adequate (explained in succeeding paragraph), the electrons are driven into the
second TiO2 layer of the DALS and are absorbed at the high surface area
TiO2/Zirconia interface. Schottky barrier, which is developed when metal and
semiconductor comes in contact, faced by hole and electron at the Ti-TiO2
interface for the flow is the same. When applied potential from solar cell is
enough to over comes this Schottky barrier, the electron starts to flow from Ti
plate to TiO2 nanotubes of DALS (hole starts to flows from Ti plate to TiO2
nanotubes of SASL). Platinum counter electrode of solar cell which is connected
to the SALS of the capacitor accepts electrons from Ti to replenish the electrolyte
hence Gratzel’s cell is complete in its work flow.
2.5. Development of an “Integrated system”
2.5.1. Anodization
Anodization technique was used to create TiO2 Nanotube on Ti plate. It is
an electrochemical passivation process used to develop a natural oxide layer on
the metal surface. It is a simple and cost-effective electrochemical process. A
major advantage of anodization is the feasibility to tune the size and shape of
nanotubular arrays to the desired dimensions, meeting the demands of specific
applications by means of controlled anodic oxidation of the metal substrate. The
processing conditions affect the growth rate, morphology, density, uniformity,
crystallinity, thickness etc. of the oxide layer. Different parameters like electrolyte
composition, temperature, voltage and anodization time on the anodic film
formation have been investigated in detailed by various groups [26-27]. In our
study, the anodization method followed is as per the literature [28] in an organic
electrolyte containing Hydro fluoric acid (HF)/Dimethyl Sulfoxide (DMSO) at a
constant potential for different time duration, resulted in well ordered array of
TiO2 nanotubes on Ti plate.
Commercially pure titanium plates (98%, grade 2) were polished to
nanoscale with alumina suspension of 300 and 50nm using beta Buehler grinder
polisher. Further, the samples were ultrasonically cleaned in acetone and isopropyl

alcohol sequentially and then air-dried. The electrochemical cell used for
anodization consists of metallic titanium plate (anode) and platinum electrode
(cathode) connected to a regulated dc power supply (Figure 2.6 (a)). The samples
were potentiostatically anodized using DMSO/HF at 40 V.
Generally accepted mechanism for the formation of TiO2 nanotubes are:
1. Field assisted oxidation of Ti metal to form TiO2
2. Field assisted dissolution of Ti metal to form TiO2
3. Chemical dissolution of Ti and TiO2 due to etching by fluoride ions
Equation (2.5) and (2.6) represents oxide layer formation and (2.7) and (2.8)
represents the dissolution reaction.
2H2O O2+ 4H + 4e- ------------------------- (2.5)
Ti + O2 TiO2 -------------------------- (2.6)
TiO2+ 6F- + 4H+ [TiF6]2- + 2H2O ------------------ (2.7)
Ti4+ + 6F- [TiF6]2- ------------------------ (2.8)
The formation of nanotubes in fluoride containing electrolytes is the result of the

interplay between three simultaneously occurring processes-field assisted
oxidation of Ti metal to form titanium dioxide, field assisted dissolution of Ti
metal to form titanium dioxide and chemical dissolution of Ti and TiO2 due to
etching by fluoride ions. The evolution of oxygen (O2) is observed at the
beginning of anodization and the titanium surface was electrochemically oxidized
to form a oxide layer (barrier layer) which was described by electrode reactions
equation 2.5 and 2.6, The increasing in the thickness of the barrier layer gave rise
to an ohmic resistance proportional to the thickness of the barrier layer. The
presence of F− ions attaches TiO2 and drives the chemical dissolution of oxide
layer and it forms a complex of titanium (TiF6 2-) denoted by reactions 2.6 and 2.7

[28]. The growth of TiO2 film is by anodic oxidization takes place not at the
outside surface of the oxide film but at its interior surface which adjoins the
underlying metal (at Ti/TiO2 interface), while the chemical dissolution proceeds
mainly at the outside surface of the film. Thus, the formation of TiO2 nanotubes is
the result of interplay between these simultaneously occurring reactions [29-28].
The anodization set up used for preparing SALS and DALS are different
which is shown in Figure 2.6.
(a) (b)
Figure 2.6: (a) Single side anodization set up (b) double side anodization set up.
For preparation of DALS another anodization set up is used, in which two

platinum rods are placed facing each face of Ti plate as shown in figure 2.6(b).
The voltage is applied across the Ti and Platinum wire, both the platinum wires
are shorted, which ensures equal field distribution on either face of Ti plate; hence
equal growth of TiO2 nanotubes are seen on either side. The anodization
conditions for DALS and SALS are the same, the electrolyte prepared contains
48wt% aqueous HF: DMSO in 1:49 volumetric ratio and anodization carried at 40
V for 48 hrs.
2.5.2. Characterization of TiO2 nanotube
i. SEM
Figure 2.7(a) shows the cross sectional SEM image of Double side
anodized Titanium foil (25 m thickness) for long time (96 hrs) in order to
distinguish Ti and TiO2 nanotube. It is clearly visible in SEM that the nanotubes
are grown on either side of Ti foil are of almost equal length (~12-14 µm) which
indirectly shows that the growth rate of nanotube is same because of the equal

field distribution. Figure 2.7(b) (c) shows the magnified image of TiO2 nanotube
and its lateral view.
Figure 2.7: (a) SEM image of double side anodized Titanium plate where it is
clearly visible that nanotubes grown on either side are almost equal in length (~ 12
µm, 96 hrs) which indirectly shows that the growth rate of nanotube is same
because of the equal field distribution. (b) & (c) shows the magnified image of
TiO2 nanotube and its lateral view.
After anodization, Ti plates were cleaned in distilled water and annealed at

400 0C for 30 minutes to convert it to anatase phase. XRD pattern of the anodized
plate is shown in Figure 2.8 and which shows that TiO2 exists in anatase
crystalline phase [30]. Anatase phase is the preferred due to the difference in the
flat-band potential of anatase and rutile. Because the anatase conduction band is
0.2 V more negative than that of rutile, a larger maximum photovoltage can be
obtained on anatase than on rutile if the same redox mediator is used [31-32].
A report shows there is a synergistic effect exists between anatase and
rutile when mixed-phase TiO2 nanocomposites are used in DSSCs. Koo and co-
workers synthesized TiO2 nanorods with varying particle sizes and crystal phases

and found that the mixed-phase TiO2 demonstrated higher solar conversion
efficiency than pure-phase anatase or rutile in DSSCs [33] Contradictory results
have been reported in the literature, in which pure anatase showed higher
efficiency as the photoanode than mixed-phase TiO2 [34-35]. In these studies, the
crystal phase was varied together with other parameters including the particle size,
morphology, and mesoporosity of TiO2 materials. Because these parameters could
potentially influence dye adsorption and charge transfer, a conclusive comparison
between pure- and mixed-phase TiO2 materials as DSSC photoanodes cannot be
obtained based on these studies.
Figure 2.8: XRD pattern of the anodized Ti plate after annealing, symbol A
denotes peaks corresponding to anatase face with (hkl) indices for different planes
(JCPDS 84-1286), Ti denotes peaks for Titanium.
2.5.3. Assembly of Integrated structure

Annealed plates were treated with 0.2M aqueous solution of TiCl4 [36] and
dried in 100 oC in oven. The treatment with TiCl4 was used because of a previous
study, which showed increased capacitance by the formation of TiO2
nanoparticles [37] as well as an increase in the PV efficiency. This study is
carried using eosin gelblich dye. The UV-Visible absorption spectrum of Eosin
gelblich dye is shown in Figure 2.9, spectra shows a narrow absorption band
width and maximum absorbance at wavelength 516 nm. Narrow band absorbing
dye is not a good candidate as a photon absorber in DSSC. This dye is not an
efficient candidate for the PV performance but it is cheaply and easily available in

market and was selected for the initial studies. Later on, these studies were
extended with the best performing Ruthenium based dye N719.
2.0
516.6nm
1.5
Absorbance
1.0
0.5
0.0
200 300 400 500 600 700 800 900

Wavelength (nm)
Figure 2.9: UV-Visible absorption spectrum of Eosin gelblich dye.
One side of DALS was sensitized overnight with Eosin gelblich dye and a
thin dielectric layer of ZrO2 (Sigma Aldrich) was deposited on the other side;
Figure 2.10 shows the SEM image of ZrO2 on TiO2 nanotubes. It is clear from the
SEM that the dielectric layer has uniformity over the nanotube substrate.
Figure 2.10: SEM images of the uniform layer of ZrO2 on TiO2 nanotubes
0.3M lithium iodine/ iodide [Sigma Aldrich] in ethylene glycol was taken
as the electrolyte for the solar cell. Electrolyte was dropped between dye coated
DALS and platinum coated ITO counter electrode to complete the solar cell part.
SALS was placed on the top of the dielectric layer to assemble the capacitor

structure as per Figure 2.5. A polymeric spacer is placed between the counter
electrode and the working electrode of solar cell to seal it properly so that
electrolyte leaking and shorting of working and counter electrode can be avoided.
Practically assembled cell structure is shown in Figure 2.11.
Figure 2.11: Practically assembled structure of integrated solar cell with

capacitor. Initially, the solar cell and capacitor were characterized separately and
then photo charging and discharging of an integrated device were carried out.
2.5.4. Device characterization of isolated DSSC

I-V characterization is carried under a light irradiation of 100 mWcm−2
with a 500 W xenon arc lamp combined with cut-off filters eliminating ultraviolet
and infrared light. The I-V characteristics of solar cell is shown in Figure 2.12,
measured parameters are open circuit voltage Voc = 0.42V, short circuit current
density Jsc = 970 µA/cm2 and efficiency  is 0.21%.

Figure 2.12: I-V characteristics of solar cell with eosin dye, open circuit voltage
Voc = 0.42 V and short circuit current density Jsc = 970 µA/cm2.
2.5.5. Device characterization of isolated capacitor
Charging and discharging of capacitor separately (without the integration) is

carried out at a constant current and its voltage variation with time is noted. The
capacitance, C, of a capacitor can be calculated by studying its voltage variation
with time under constant applied current and is given by [38]
C I --------------------------- (2.9)
(dV/dt)
Here I is the externally applied charging current to the capacitor, dV/dt is

the slope of the straight-line portion of the charging curve.
Figure 2.13: Voltage -Time graph of Ti-TiO2 -ZrO2-TiO2 -Ti capacitor at a

constant charging and discharging current.
The capacitor was constructed with Zirconia deposited between two SALS
electrodes (48 hrs anodization) and when the external current was applied the
voltage at first increases very steeply, that is, dV/dt is high or capacitance is very
low indicating little storage, The obtained capacitance is 140 µFcm-2 was
measured at 10 A/cm2 (Figure 2.13). The literature reported value [39] for
sputter-coated zirconia was 0.15 µF/cm2, order of magnitude smaller. The
difference was attributed to the presence of the Titania nanotube layer on the

titanium electrodes. The subsequent chapter reveals the role of TiO2 nanotubes on
capacitance.
2.5.6. Device characterization of integrated structure
The equivalent circuit of the integrated structure is a DSSC in parallel with
a capacitor. Under illumination, DSSC develops an open circuit voltage Voc and a
short circuit current Jsc. PV output can be taken between the PV counter electrode
and the metal layer of the DALS while the capacitor output can be taken between
the metal layer of the DALS and the metal layer of the SALS. Thus, there is true
integration of the solar cell and the capacitor in a single thin film device. Before
studying the detailed characterization of an integrated structure I would like to
give a brief discussion on how electron flows from solar cell to capacitor or the
minimum potential that solar cell should possess to make the integration of a
storage unit possible. The electron in solar cell wouldn’t flow spontaneously
unless and until an electro-motive-force (EMF) is applied. Here electron has to
cross the solar/capacitor junction which is developed between Ti (the current
collector in solar cell) and TiO2 (High surface area electrode in capacitor), this
junction offers barrier potential for the flow of electrons. A necessary condition
for the spontaneous storage is that solar cell should provide enough potential to
overcome this barrier to make electron to flow from solar to storage cell, this
barrier potential is called Schottky barrier.
2.6. Detailed characterization of Schottky barrier between Ti metal and TiO2
nanotube
When a metal (Ti plate) and semiconductor (TiO2 nanotubes) layer comes
in contact, a Schottky barrier potential (S.B) [40] is generated across the
interfacial junction that prevents charge flow from the metal to the semiconductor.
(S.B: Difference between the Fermi level of the metal and the conduction band
edge of the semiconductor) In order for the electrons to travel to the Titania layer
from the metal of the DALS an additional external potential difference provided
by the PV must be larger than the Schottky barrier. We show that this is indeed
the case for the present design so that charge flow to the capacitor can occur
spontaneously until the capacitor is fully charged. Experimental and theoretical
methods were used to measure the Schottky barrier potential between the Ti and
the TiO2 nanotube layer.

2.6.1. Physics behind Integration of DSSC with capacitor

In our model which shown in figure 2.5, DSSC is connected to the
capacitor via a double side anodized Ti plate, this Ti plate act as the current
collector of solar cell and TiO2 nanotube acts as the high surface area electrode of
the capacitor. An issue arises that electron wouldn’t flow spontaneously from a
metal to semiconductor where it faces a potential. Metal semiconductor contact
forms an interfacial barrier which regulates the flow of electrons from DSSC to
capacitor. The photo generated electrons in DSSC have to travel through the Ti
plate (DASL) and to cross Ti-TiO2 barrier at the capacitor side to reside at the
high surface area interface between TiO2 nanotube and ZrO2 dielectric. This part
deals with the detailed study on the mechanism of charge transport from DSSC to
the high surface area dielectric based capacitor.
Study on the metal and semiconductor barrier potential is important here
because it governs the flow of electron from solar cell to capacitor. For
macroscopic n-type semiconductor materials in contact with metals, a depletion
layer forms at the junction between the two materials and a potential develops
across the junction, this potential barrier is responsible for controlling current
conduction [41] through the junction. The initial charge transport between n-type
semiconductor and metal is through electron flow from n type semiconductor to
metal so as to equilibrate Fermi energy levels of the system. There are reports on
junctions with adjustable electronic properties between bulk semiconductors and
quantized electro-active materials, thus nanoparticle-semiconductor interfaces are
relevant for the fabrication of Schottky diodes with well-defined or actively
tunable barrier heights [42]. When a quantum dot (QD)-metal interface forms, an
equilibration of fermi level occurs between the systems and a nano-level
Schottkey barrier forms. However, if the diameter of the QD is less than depletion
layer thickness there is no electron significant depletion layer within the QD to
impede electron transfer [43]. These Schottky barriers severely limit transistor
conductance in the ‘ON’ state, and reduce the current delivery capability-a key
determinant of device performance [44]. These studies show the dependency of
interfacial properties of semiconductor-metal junction on nature and morphology
of the semiconductor layer.

When a metal and semiconductor comes in contact, an interfacial layer

forms and band bending at the interface occurs that generates a barrier potential
across the junction. Fermi-level equilibration (Figure 2.14) between the metal and
the semiconductor yields a space-charge region in the semiconductor and hence an
electrostatic barrier to charge flow. Figure 2.14 shows the Flat-band alignment
diagram of semiconductor-metal interface when they come in contact. Schottky
barrier is a function of  M
and, here  depends on the position of conduction
band edge.
Figure 2.14: Schematic representation of the formation of Schottkey barrier upon

metal semiconductor contact.
 M
is the work function of metal (4.33 eV for Ti metal) in contact
 is the electron affinity (which is the separation between vacuum level and
conduction band edge) of the semiconductor.
The barrier height  s
is defined as the potential difference between the Fermi
energy of the metal and the band edge where the majority carriers reside in
semiconductor. Schottky barrier can be calculated by the equations given below.

  
s M
------------------------------------------------ (2.10)
Where  is the Schottky barrier.

s
Upon the contact of metal on semiconductor, the Fermi level equilibration

occurs via downward shifting of Fermi level of semiconductor. This generates an
internal electric field [45]. The internal electric field causes a varying potential
and hence band bending occurs.
The depletion width is given by:
2 ( E fs  E fm )
W  ------------------------------------------------ (2.11)
Nd e2
Where W is the depletion layer width,  is the permittivity of electric field,
N d is the donor concentration. Efs, Efm are the fermi levels of semiconductor and
metal before contact.
Here electrochemically synthesized nanotubes on titanium metal formed a
natural Schottkey barrier 48 hrs anodized sample with which we proved the
concept of integration (Figure 2.14) is taken and we studied the magnitude of S.B
(Schottky Barrier) by some indirect experiments. With reduced dimensionality
(wall thickness) of the semiconductor nanotube structures we have observed band
gap expansion and band edge quantum confinement effects. At voltages greater
than Schottky barrier, Charges can travel along the nanotubes and reside at an
interface between the nanotubes and a high- dielectric such as Zirconia (ZrO2).
This property was utilized to develop high surface area solid-state capacitors.
2.6.2. Different techniques for Schottky barrier measurement
The position of conduction band (C.B) and valance band (V.B) edge of the
semiconductor affects the Schottkey barrier. Cyclic voltammetry can be used to
find out the C.B (Conduction Band) of the TiO2 nanotube, which carried out in
conducting electrolyte. From the reduction potential, conduction band (C.B) edge
could be calculated as:
E c  ( E reduction  E ref ) -------------------------------------------- (2.12)
Here, Eref is potential of reference electrode Ag/AgCl, which is 4.7 V.
The conduction band edge and Fermi level is related by:

n 
E f  E c  KT ln c  -------------------------------------------- (2.13)
 Nc 
Where E f is the fermi energy level , E c is the conduction band edge, nc is the
density of net ionized states and N c is the density of states in conduction band
(For TiO2 N c ≈ 1021 cm-3 and nc ≈ 1017 cm-3) [46-47]. Knowing the optical band
gap from UV measurements one can find out position of valence band edge.
Cyclic voltammetry:
Cyclic voltammetry (CV) was carried out in a three electrode system using
Autolab potentiostat/galvanostat; anodized Ti plate was used as the working
electrode, platinum as the counter electrode and Ag/AgCl taken as the reference
electrode. 0.1M Na2SO4 was used as the electrolyte and cyclic voltammetry is
carried out in a potential window of -1.5 to 1.5 V at a scan rate of 15 mV/S. The
fermi levels are calculated and are shown in table 1. It was observed that reduction
potential for 48 hrs anodized sample is -0.663 V (Figure 2.15).
Figure 2.15: Cyclic voltammetry of 48 hrs anodized sample is carried out in

0.1M Na2SO4 in a potential window of -1.5 to 1.5 V at a scan rate of 15 mV/S, the
reduction potential is found to be at -0.663 V.

The C.B of TiO2 nanotube is situated at 4.037 eV below the vacuum level and the
position of Fermi level is calculated using equation (2.13) and found to be 4.273
eV below the vacuum level.
UV-Visible spectroscopy:
UV-Visible spectroscopic (Figure 2.16) study is carried out to find the
band gap (B.G) of the TiO2 nanotube, which corresponds to the minimum energy
required to start absorption. UV-Visible spectroscopic (Perkinelmer lamda 750)
study is carried out in an integrating sphere set-up, which could find the
absorption for an opaque substrate based on reflection from the surface.
Absorption for the anodized samples on Ti plate was carried out; B.G is the
energy corresponding to the onset wavelength of absorption. The onset of
absorption is at 385 nm which corresponds to band gap energy of 3.23eV. From
B.G and Conduction band (C.B) edge calculated position of Valance band edge is
at -7.29 eV. Schottkey barrier is calculated as per equation 2.10 and is found to be
0.301 V. Thus we can conclude that the Voc, the open circuit voltage of solar cell
should be sufficient enough to overcome this barrier potential to start flow of
electron to TiO2 nanotube.
Figure 2.16: UV-Vis absorption spectra of 48 hrs anodized TiO2 nanotube and
onset of absorption (corresponding to bandgap) is at 385 nm which corresponds to
band gap energy of 3.23 eV.

Electrochemical impedance analysis:

Electrochemical impedance analysis of titanium dioxide nanotubes on Ti
plate was carried out using Autolab potentiostat/galvanostat and data recorded
over a frequency range of 0.1 Hz to 1 MHz with an ac voltage of amplitude 10
mV. Impedance analysis was carried out applying a constant bias at open circuit
voltage (OCV).
Figure 2.17: Impedance spectra of 48 hrs TiO2 nanotube on Ti plate.
The result of an impedance analysis is represented by Nyquist plot (figure

2.17). The presence of an arc in the plot represents an electrochemical interface
existing in the system [48-49]. Resistance across the junction is directly related to
depletion layer width (equation 2.11) and Schottky barrier [21]. Experimental
results on interfacial resistance are shown in figure 2.17, from impedance analysis,
the radius of the circle shows the interfacial resistance of Ti-Titanium dioxide
junction nearly 10 .
Current-Voltage (I-V) study in Scanning Electro Chemical Microscopy
(SECM):
I-V study of TiO2 nanotubes are carried out in Autolab potentiostat-
galvanostat/Scanning electrochemical microscope (SECM, make: Sensolytics)
with the help of 10 µm wider platinum microelectrode and an ionic conducting
electrolyte. Ti plate, on top of which Titanium dioxide nanotube is grown, is taken
as one electrode and platinum microelectrode as the second electrode. 0 V to 0.4
V is applied and current value noted. We have experimentally verified the

variation in Schottky barrier from I-V characteristics of nanotube. Voltage is

applied between platinum and titanium. Figure 2.17 shows the I-V behavior of
TiO2 nanotubes; barrier potential obtained from experiment is 0.28 V. This shows
the versatility of using SECM measurements for estimation of the Schottky
barrier.
Figure 2.18: I-V behavior of TiO2 nanotubes in SECM; barrier potential obtained
is 0.28 V.
For this purpose a separate experiment carried out, a potential difference

was applied in between the Ti and the TiO2 nanotube layer on an anodized plate
and the resulting current output through the Ti/TiO2 interface was measured. The
threshold voltage at which a measurable current obtained was equivalent to the
Schottky barrier potential. The I-V curve is shown in Figure 2.18 which indicated
a barrier breakdown voltage of 0.28V (the Schottky barrier potential) which in this
case was lower than the open-circuit voltage of the PV (Voc= 0.42 V, Jsc= 970 µA
cm-2). This result shows that the barrier potential that an electron experiences
while crossing the Ti-TiO2 junction is ~0.28 V. Thus the Voc of the solar cell
should be higher than this potential to make integration of storage unit possible,
which is indeed the case.

2.6.3. Effect of Schottky barrier on dimensionality of TiO2-NT

In order to study the effect of dimensionality of nanotube on Schottky
barrier, similar set of experiments are carried out with different time anodized
sample(18 to 72 hrs) and obtained result shows S.B (Schottky barrier) is a
function of nanotube thickness dimension and shows lesser barrier potential for
longer time of anodized sample (sample having thinner walled nanotubes).
Figure 2.19: SEM images of 18 and 48 hrs anodized samples.
SEM images (Figure 2.19) clearly shows that as the time of anodization
increases the wall thickness of nanotube is reducing and results show that as the
time of anodization increased, the wall thickness of the nanotube decreased from
41 to 26 nm. As the wall thickness of nanotube reduces the electron would be
facing more space confinement along the width of the wall; this is the reason for
ballistic transport of electron in 1-D (one dimensional nanostructure). We could
expect more quantum confinement effect on account of the thinning of nanotube
wall.

Figure 2.20: Lateral SEM images of TiO2 nanotube for different time of
anodization (a) 18 hrs (b) 48 hrs (c) 72 hrs
SEM images (Figure 2.20) clearly shows that as the time of anodization
increases from 18 to 72 hrs the length of nanotube is found to be increasing from
2.75 to 7.32 μm. Thus the dimensionality both in lateral and longitudinal wise
changes as the time of anodization varies. Longer nanotube the extent of quantum
confinement is higher because of the much reduced wall thickness. Electrons are
constrained to travel in the lateral direction (thickness direction) and forced to
travel balistically along the longitudinal direction. Because of the lower schottky
barrier electrn transport is much enhanced in the longer nanotube.
Cyclic voltammetry is carried for all the samples to find their reduction
potential and found that reduction potential increasing from -0.735 V to -0.633 V
(Figure 2.15) as time of anodization goes from 18 to 72 hrs. Conduction band
edge is moving down or becoming more negative with respect to vacuum energy
level from -0.396 to -0.406. UV absorption spectra of samples are found to vary
from 393 to 384 nm (Figure 2.21(a), (b)) (B.G changes from 3.16 eV to 3.24 eV).
From the Band gap and position of C.B edges, the position of V.B edge is
calculated and found to vary from -7.13 to -7.3 eV. From all these observation

(Figure 2.21) and calculations, a blue shift of 10 nm occurs in absorption as the

time of anodization varies from 18 to 72 hrs. I-V study for each sample is carried
out and graph is shown in figure 2.21(e), the variation of S.B with time shows S.B
decreases from 0.33 V to 0.22 V. Variation of S.B by both experiment and by
indirect methods and fermi levels were tabulated.
(b)
(a)
(c) (d)
(e)

Figure 2.21: (a) & (b) Cyclic voltammetry of 18 to 72 hrs anodized samples in
0.1M Na2SO4 at a scan rate of 15 mV/s (c) UV-Vis absorption spectra of 18 to 72
hrs anodized TiO2 nanotubes (d) Onset of absorption (corresponding to bandgap)
wavelength versus time of anodization plot (e) I-V behavior of 18 to 72 hrs
anodized TiO2 nanotubes with SECM.
Table 2.1 and table 2. 2 shows how C.B, V.B, S.B varies in accordance
with time of anodization, it is clear that 18 hrs anodized sample has lesser barrier
potential compared to 72 hrs anodized samples.
Table 2.1: Shows the change in absorption wave length, band gap, conduction
band width and valance band gap with time of anodization

Table 2.2: shows the variation in reduction potential and fermilevel alignments
for 18 hrs to 72 hrs anodized sample
Table 2.2 clearly shows the variation in band gap and conduction/valence
band edge alignments for 18 hrs to 72 hrs anodized sample. Observation shows as
anodization time changed from 18 to 72 hrs there was a blue shift (~10 nm) in the
absorption wavelength and increase of the band gap energy confirming quantum
confinement effect upon thinning of the nanotube walls. Also, there was a
corresponding negative shift of the conduction/valence band edges to
accommodate the widening band gap. The thinning of the nanotubes thus resulted
in a reduction of the Schottky barrier at the titania nanotube/Ti interface allowing
for easier electron capture from the Ti metal into the titania nanotubes when the
applied potential from the solar PV is greater than this barrier height. Resistance
across the junction is directly related to depletion layer width (equation 2.11) and
Schottky barrier, thus we could expect reduction in interfacial resistance for
longer time anodized sample. The depletion width is given by the equation 2.11
which also shows a reduction in interfacial resistance with time of anodization.

Electrochemical impedance analysis:

From impedance analysis (Figure 2.22), radius of the circle shows the
interfacial resistance of Ti-Titanium dioxide junction. For longer nanotubes (Time
of anodization -72 hrs) it is about 8  whereas for shorter nanotubes (Time of
anodization-18 hrs) it is nearly 15 .
Figure 2.22: Impedance spectra of TiO2 nanotube on Ti plate
Metal and n-type semiconductor contact makes the electrons to flow from
n-type semiconductor into the metal in order to equilibrate the Fermi levels; this
charge transfer yields a space charge region within the semiconductor due to
uncompensated donor atoms. The internal electric field causes a varying potential
and hence band bending occurs. Longer nanotubes show lower Schottky barrier
resulting from the thinner depletion layer, thus the resistance offered by the
junction for longer nanotubes would be smaller. Impedance analysis showed a
result which supports this statement. All of the above studies show the existence
of Schottky barrier potential between the TiO2 nanotube and Ti interface and has
been characterized in detail. One of the applications based on this property is the
development of dielectric based solid state capacitor incorporating high surface
area electrodes; which is discussed later in detail.
From above study we can conclude by stating that the development of the
Schottky potential barrier across the interface is related to dimensionality (lower
wall thickness) of nanotube. With reduced dimensionality of the nanotubes, we
have observed band gap widening and band edge quantum confinement effects.
There is a widening of the band gap and corresponding movements of the band

edges. The Schottky barrier and interface resistance is also lowered considerably
promoting ballistic transport along the nanotube length. Integrated cell with long
time anodized sample showed faster charging than short time anodized sample;
this supports the lowering of barrier potential for thinner walled nanotube.
2.7. Device characterization of integrated cell with 48 hour of anodization
When the combination device was exposed to light the counter electrode
of solar cell is connected to the SALS of capacitor. The charges generated in the
PV section were stored in the capacitor leading to an increase in the capacitor
voltage as shown in Figure 2.23(a). This was as opposed to charging by an
applied external current as shown in Figure 2.13.
In this case of charging through the PV using a sun simulator, the voltage
across the capacitor instantaneously rises to at first to Vo (corresponding to the
Schottky barrier voltage) and then sigmoidally increases to Vmax , where Vmax is the
maximum voltage that the capacitor can develop (Figure 2.23(a)). Vmax is
approximately 60% of Voc indicating good storage capacity of the capacitor. The
solar cell illuminated for 100 seconds and the light is closed off and solar cell is
disconnected and voltage across the capacitor noted for 1500 seconds and found
that voltage remains constant.
Figure 2.23: (a) Voltage variation upon photo charging in capacitor. The solar
cell illuminated for 100 seconds and solar cell is disconnected and voltage across
the capacitor noted for 1500 seconds and found that voltage remains constant (b)
shows the current variation with in integrated solar cell time upon illumination.
The rate of charging and discharging is dependent on the polarization and

depolarization ability of the dielectric material (ZrO2) used. Upon forced

discharging, using an externally applied current of 1 µA/cm2, an initial rapid

discharge rate was observed which was followed by a slower discharge at longer
times (see Figure 2.23(a)). Voltage across the capacitor retains its maximum value
even if the illumination for the DSSC is discontinued. Figure 2.23(b) shows
current-time behavior of solar cell in which current increases rapidly on
illumination and reaches maximum and remains constant as long as illumination is
present. This proves the independent functioning of the PV and storage
components of the integrated device. From all the above mentioned studies we
have shown a novel integrated thin film device combining a PV and a capacitor
wherein both are capable of independent operation as well as combined operation.
The optimization of the PV layers and the capacitor layers can further improve the
separate efficiencies of the two components, namely, the generation efficiency of
the PV and the storage efficiency of the capacitor. We have developed an
integrated structure with 72 hrs of anodization and photo charging and discharging
carried out. From the figure 2.24, it is evident that the capacitor achieves
maximum voltage quickly compared to the 48 hrs anodized sample. Illumination
turned off after 100 seconds and voltage variation with time is noted and it is
found to be remaining constant even after shutting light off. This cell shows a fast
charging rate compared to our previous integrated cell; this could be due to the
low interfacial resistance offered by the Ti-TiO2 junction on account of thinner
walled nanotubes. The voltage is found to be retaining its maximum even under
dark and shows discharging upon the application of a discharging current. Here 1
µA is applied after 1000seconds and discharging is noted and found that sudden
IR drop of 0.2 V followed by a gradual decay.

0.45
illumintion turned off Discharging current 1A
0.40
0.35
Voltage(V)
0.30
0.25
0.20
0.15
0 500 1000 1500 2000
Time(sec)
Figure 2.24: Photo charging and discharging of 72 hrs anodized integrated

structure. Illumination turned off after 100 seconds, 1 µA is applied after 1000
seconds for discharging and voltage variation with time is noted.
2.8. Optimization of dye sensitized solar cell and dielectrics of capacitor

This part of the study deals with the optimization of a DSSC and synthesis
of two types of dielectric materials for capacitor. Even though the focus of this
work is basically on the integration of a storage unit with a DSSC and
development of different storage units, little effort is put to improve the solar part
so that the performance of integrated storage unit can be studied in detail. Dye-
sensitized solar cells have recognized as a potential low-cost alternative to
conventional silicon solar cells due to their high power-conversion efficiency
jointly with 'low-tech' fabrication processes [50]. The role and significance of
different layers of DSSC is already discussed in the sections 1.2.5 and 2.1. Dye,
Electrolyte, Counter electrode, Wide band gap semiconductor morphology are
some areas of interest which would enhance the total performance of the cell.
Efficient charge separation requires the electron injection kinetics to be faster than
decay of the excited state of dye to ground state. Efficient cation transport to the
redox electrolyte requires the dye cation re-reduction by the redox couple to be
quicker than recombination between injected electrons and photogenerated dye
cations [51]. After all, efficient charge collection requires charge recombination

between injected electrons and oxidised redox species in the electrolyte to be

slower than transport of these species to the working and counter electrodes,
respectively.
Second part of this study shows the synthesis of two nano dielectrics ZrO2
and BaTiO3 for the development of dielectric capacitor. A dielectric is a non-
conducting material when inserted between the conducting plates it gets the
capability of charge storage or it becomes a capacitor. The maximum voltage that
can be applied to a capacitor without causing a discharge depends on the dielectric
strength. The dielectric strength equals the maximum electric field that can exist
in a dielectric without electrical breakdown. Rated voltage represents the largest
voltage that can be applied to the capacitor without exceeding the dielectric
strength of the dielectric material in the capacitor.
2.8.1. Optimization of DSSC
TiO2 nanotubes as a wide band gap semiconductor not only provides high
surface area for dye adsorption but also facilitate ballistic charge transport of
electron. Initially Eosin gelblich dye was selected as a photon absorber, figure 2.9
shows the absorption spectra which has narrow absorption band width and
maximum absorption occurs at 516nm. Anodization is carried out for 12 hrs and
annealed at 450oC, treated anodized Ti with aqueous TiCl4 and dipped in eosin
dye over night. Iodine/Lithium iodide in acetonitrile was taken as the electrolyte
and platinum coated Indium tin oxide coated glass plate was taken as the counter
electrode. Cell is assembled by placing a spacer and counter electrode (Pt/ITO)
and sealed to prevent leaking of electrolyte; finally liquid electrolyte is dropped in
between. The device was illuminated with light of 100 mWcm-2 and its Current-
Voltage (I-V) was noted and is shown in figure 2.25. The drawback of Eosin dye
is that it can absorb very narrow portion of incident light since its absorption has
narrow band width.

Figure 2.25: Shows The I-V of solar cell with Dye: Eosin, Electrolyte:
Iodine/Lithium Iodide (0.3M), Counter electrode-Pt/ITO, Voc=0.38 V, Jsc=1.9
mA/cm2,= 0.25%.
Figure 2.26: I-V characteristics of solar cell with Dye: Ruthenium N719,
Electrolyte: Iodine/Lithium Iodide (0.3M), Counter electrode-Pt/ITO, Voc=0.47 V,
Jsc=1.13 mA/cm2, =0.45%.
The dye is replaced by Ruthenium N719 which shows wide range of

absorption in the visible range of light. When N719 interacts with light more
photo electron would be released and it may increase efficiency of the DSSC. The
I-V characterization of DSSC was studied and the efficiency shown an
improvement to 0.45% (Figure 2.26).
Dye adsorption on nanotube is directly proportional to surface area of
nanotube. The time of anodization in increased to 48 hrs the length of nanotube

increases from 3 to 7 m hence longer time anodized tube would provide better
surface area. Solar cell is assembled with 48 hrs anodized sample and The I-V
characterization of DSSC was studied. It shows an improvement in the efficiency
1% (Figure 2.27). This improvement could be attributed to surface area of the
tube.
Electrolyte: Iodine/Lithium Iodide (0.3M), Counter electrode-Pt/ITO , Voc=0.62
V, Jsc=3 mA/cm2, =1%.
It was already stated that for efficient cation transport to the redox
electrolyte requires the dye cation re-reduction by the redox couple to be quicker
than recombination between injected electrons and photogenerated dye cations
that is rate of redox reaction faster, The regeneration of the oxidized dye occurs in
the nanosecond (10-9) range, which is normally 100 times quicker than any
recombination reaction and about 108 times faster than the intrinsic lifetime of the
oxidized dye. Conductivity of the electrolyte is a main factor which retards the
flow of electron. The conductivity hence short circuit current can be enhanced by
introducing ionic redox electrolyte per [52]. Ionic liquids are room temperature
molten salts that entirely consist of cations and anions. By utilizing their
characteristics such as non-volatility, non-flammability, high ionic conductivity,
and gel-forming property with polymers, [53] electrolyte is prepared as: 0.6M 1-
butyl-3-methylimidazolium iodide, 0.03M iodine, 0.1M Guanidinium thiocyanate,

0.5M tert-Butylpyridine in acetonitrile/valaronitrile (85:15 volumetric ratio).The

cell is assembled and characterized with this electrolyte. We could obtain
maximum efficiency of 3.58% with Jsc 9.1 mA/cm2 and Voc 0.725 V which
shown in figure 2.28.
Electrolyte: Ionic Iodine/Iodide, Counter electrode-Pt/ITO, Voc=0.75V, Jsc=9
mA/cm2,=3.58%.
The Difficulty of the DSSC technology exists in ensuring the stability,

packing, leakage reproducibility and ample durability of the cell. Practical
lifetimes of DSSCs are dangerously affected by the gas barrier ability of sealer,
electrolyte composition and material of sealer. The interface of sealer and
electrode substrate is often involved in the leakage of components (solvents of
electrolytes). But its ease of fabrication made us to start this study with DSSC,
once the working is proved the same concept can be extended to other solar cell to
make better integrated modules.
2.8.2. Development of dielectric capacitor
A dielectric is a nonconducting material, when it is inserted between the
conducting plates of a capacitor, the capacitance increases. The capacitance of a
capacitor with a dielectric is C= Ɛr Ɛ0A/d where Ɛr is the dielectric constant of the
material, d is the separation between plates. The maximum voltage that can be

applied to a capacitor without causing a discharge (or in other way the maximum
electric field it can with stand without allowing conduction through it) depends on
the dielectric strength of the dielectric. Examples of some dielectric materials are
Air, Water, Paper, Paraffin, Zirconia, Barium titanate etc. Ceramic materials
exhibit large nonlinear optical coefficients and large dielectric constants, these
effects are dependent on structure and size. Efforts have been expended in the
controllable synthesis of crystalline materials and thin films of these ceramic
materials. In order to prepare ceramic nanocrystalline powders, several methods
such as sol-gel, co-precipitation and hydrothermal process are well known.
Hydrothermal synthesis is reported to be a soft chemical route with an important
advantage like the formation of phase pure products at low temperature.
Hydrothermal process was found most preferable because in this method crystal
size can be controlled and miniaturized by altering the process conditions. The
reaction such as hydrolysis, co-precipitation, oxidation, decomposition, and
complexation can be performed using hydrothermal method.
Figure 2.29: Image of Hydrothermal reactor
2.8.2.1. Zirconia
Zirconium dioxide (Zirconia) is one of the promising materials widely
used as a dielectric (Ɛr~25). In previous section (2.5.5), commercially purchased
ZrO2 was used and doctor bladed to get dielectric layer for capacitor. But the
method of doctor blading doesn’t ensure the reproducibility of the film thickness
which matters in capacitance. It is generally believed that the smaller the grain
size, the smoother the surface morphology and the better adhesion to the substrate

for thin-film materials. But it’s reported that the dielectric constant can be reduced
effectively by reducing the grain size from the micrometre scale to the nanometre
scale (~160 nm). The physical mechanism responsible for the grain size effect on
the dielectric constant can be explained as the change of the crystal field caused
by surface bond contraction. Nanostructured material has an enhanced crystal
field due to its surface bond contraction and the rise in the surface area-to-volume
ratio. Decreasing the particle size increases the crystal field and subsequently
decreases the dielectric constant. Even though size reduction reduces the dielectric
constant, it enables a better control and reproducibility over dielectric layer.
i. Preparation of nano Zirconia by recrystalization
We selected hydrothermal route for the synthesis of nano-ZrO2. Zirconia
was treated hydrothermally for different duration to get nanocrystalline powders.
Commercial ZrO2 procured from Sigma Aldrich was taken in a 10 M NaOH
aqueous solution (Fisher Scientific) and was transferred into a sealed teflon
container fitted in stainless steel bomb and statically heated in hydrothermal
reactor at 120°C from 36 to 60hrs (figure 2.30).
Figure 2.30: Schematic illustration of the hydrothermal synthesis of Zirconia.
The white product obtained was washed initially by dilute HCl (Fisher
Scientific), also several times with distilled water. The powder was extracted with
water and acetonitrile (Sigma Aldrich) was used as a solvent here, as expected we
obtained a uniform stable dispersion of nano ZrO2.The nanocrystalline nature of
hydrothermally prepared samples may be due to leaching of zirconia by alkali, it

forms highly disordered intermediate phase containing Zr, O and Na. When the
raw material ZrO2 is treated with aqueous NaOH, some of the Zr-O-Zr bonds may
be broken and Zr-O-Na as well as Zr-OH bonds are formed. When the material is
treated with aqueous HCl and distilled water, the Zr-O-Na and Zr-OH bonds may
react with acid and water to form new Zr-O-Zr bonds [54].
The reaction is shown below:
2ZrO2 + NaOH Zr-O-Na + Zr-O-H
ZrONa + ZrOH + H2O + HCl Zr-O-Zr + NaCl + 2H2O.
ii. Characterization of Nano-ZrO2:

Hydrothermally synthesized ZrO2 were characterized to check its
morphology and crystallinity by SEM and XRD and we confirmed the formation
of nanoZrO2.
SEM:
Figure 2.31 shows the SEM image of hydrothermally treated ZrO2 over
anodized Ti substrate, which shows the uniform coverage of dielectric film.

Figure 2.31: SEM images of hydrothermally grown ZrO2.
XRD:
The reconstruction of Zirconia is confirmed by XRD analysis (ICDD PDF
Card No: 37-1484, ICDD PDF Card No: 29-997) [55-56]. XRD diffractogram
corresponding to alkali treated zirconia reveals the occurrence of mixed phases
(monoclinic and cubic) of ZrO2. Figure 2.32 shows XRD pattern of different time
of hydrothermally treated ZrO2, it is clear that the crystallinity doesn’t change by
varying the time duration of hydrothermal treatment.

Figure 2.32: XRD pattern of hydrothermally synthesized ZrO2 (Top) 48hrs

showing crystalline planes (Bottom) for different time of hydrothermal treatment.
iii. Development of capacitor with nano-Zirconia as dielectric: Three

configurations of capacitor were prepared with Nano-ZrO2,
1. Plain Ti/ bulk-ZrO2/plain Ti
2. Plain Ti/ nano-ZrO2/plain Ti
3. Anodized Ti/nano-ZrO2/Anodized Ti
Plain Ti/ bulk-ZrO2/plain Ti: In this configuration (Figure 2.33(a)), Ti

plate of area 1X1 cm2 is acting as the electrode for the capacitor. Since dispersion
of nano-ZrO2 is stable and uniform, the dielectric layer thickness for capacitor is
maintained constant by taking equal volume and coating it over equal area for all
samples.Bulk ZrO2 is doctor bladed on titanium pate and assembled a capacitor.
The charging and discharging of the capacitor studied at constant current 1
µA/cm2 and calculated capacitance is 12nF/cm2 (Figure 2.33(b)).
Plain Ti/ nano-ZrO2/plain Ti: The average size of size of ZrO2 particle is
found out from SEM and we observed that 48 hrs hydrothermally treated sample
show smaller size of 160±3 nm. We constructed capacitor in Ti/ZrO2/Ti
configuaration with different size nano-ZrO2, and capacitance is found to be
higher for smaller particle size ZrO2 i.e, 48 hrs treated ZrO2 show higher
capacitance 472 nF/cm2. Compared to bulk ZrO2 capacitor obtained result shows

that as the size go down capacitance increases from 12 nF to 472 nF/cm2. The
smaller size is reported to have lower dielectric constant, but its rise in surface
area and decreasing layer thickness due to monolayer formation can result in an
enhanced capacitance.
Hrs Particle Size (nm) Capacitance (nF/cm2)
48 163.35 472
54 180.21 294
36 184.87 229
60 192.38 225
24 227.96 62
0 >500 (as purchased) 12
Table 2.3: variation of capacitance with size of ZrO2

(b)
(a)
(c)
(d)
(e)
(f)
Figure 2.33: (a&b) Schematic diagram and charge discharge of Ti/bulk-ZrO2/Ti

capacitor, (c&d) schematic diagram and v-t graph of anodized Ti/ anodized Ti
capacitor without dielectric, (e&f) schematic diagram and charge discharge of
capacitor with 12, 24, 48 hrs of anodized and nano-ZrO2 dielectric Ti plate with at
a constant current of 10 µA/cm2.

In variation of first configuration, the capacitor was assembled as shown in

figure 2.33(c) is the Anodized-Ti/ Anodized-Ti without Zirconia, capacitance was
measured at constant current of I=1 µA/cm2. The calculated capacitance for 24
and 48 hrs of anodization was 812 nF/cm2 and 1.1 µF/cm2 respectively. The
improvement in capacitance is nearly 1000 times compared to plain Ti/ZrO2/plain
Ti. This result shows the improvement of capacitance is due to anodization, from
the figure this can be explained on the basis of an arrangement of number of
single nanotube capacitors in parallel. This anodized nanotube capacitor might be
a collection of nano-capacitor which are in parallel so that effective capacitance
would be higher. The second configuration is shown in figure 2.33(e) Anodized-
Ti/ZrO2/Anodized-Ti, two anodized Ti plate were taken, on top of one plate nano
ZrO2 (160±5 nm) and capacitor is assembled as shown in figure 2.33(e) and found
that the capacitance is increasing. Figure 2.33(f) shows the charge discharge for
different time anodized sample in second configuration at constant current density
of 10 µA/cm2, as the time of anodization varied from 12, 24, 48 hrs; the
capacitance was found to be vary from 17 to 55 µF/cm2 respectively (17, 40 &
55). Improvement in capacitance with the introduction of nano-ZrO2 can be
explained on the basis of functioning of a composite dielectric of TiO2 and ZrO2
and distribution of charges at high surface area TiO2/ZrO2 interface and Ti/TiO2
interfaces. As the time of anodization varies the length of nanotube increase, the
different hrs anodized plates showed an increment in capacitance from 17 to 55
µF/cm2. The 48hrs anodized samples having longer nanotubes exhibited a higher
capacitance of 55μf/cm2. These studies show that size of the electrode plays an
important role in capacitance.
No Anodization time Capacitance

1 12 hrs (~3µm) 17 µF
2 24 hrs (~5 µm) 40 µF
3 48 hrs (~7µm) 55 µF
Table 2.4: Shows the variation in capacitance with length of nanotube.

ZrO2 is good dielectric but the capacitance is in µF/cm2 and the energy
density of this dielectric capacitor would be low so this capacitor can’t serve the
requirement of storing large amount of energy. We thought of introducing new
dielectric material which has much higher dielectric constant. One such material is
barium titanate, its dielectric constant r is ~500-700.
2.8.2.2. Barium titanate (BaTiO3)

The perovskite [57-62] family includes many titanates used in various
electro ceramic applications like electronic, electro-optical, and electromechanical
applications of ceramics. The crystallographic dimensions of the barium titanate
change with temperature due to distortion of the TiO6 octahedra as the
temperature is lowered from the high temperature cubic form. Because the
distorted octahedral are coupled together, there is a very large spontaneous
polarization, giving rise to a large dielectric constant and large temperature
dependence of the dielectric constant. Also the room-temperature relative
dielectric constant increases as the grain size of the fast-fired BaTiO3 ceramic is
decreased. Two different hydrothermal routes were discussed here for the
synthesis of BaTiO3
i. Ex-situ preparation of BaTiO3
Stock solutions containing Ba2+ and Ti4+ ions were prepared using
Ba(OH)2.8H2O (Local supplier) and TiO2 (Sigma Aldrich). 10 ml of 2 M solution
of barium hydroxide (Ba(OH)2.8H2O) was taken in a teflon container. The
solution was magnetically stirred at 80oC. Then 1.0 M TiO2 was added drop wise
to the above solution. The teflon container was sealed and fitted in stainless steel
bomb and statically heated in a hydrothermal reactor at 300 oC for 4 hrs. The
obtained powder was again magnetically stirred using distilled water for 6 hrs.
Complete washing of the powder was carried out several times using distilled
water and then the powder was dispersed using DMF (N, N Dimethyl Formamide)
(Fisher Scientific) as solvent.
ii. Characterization of Exsitu-BaTiO3
SEM:
From the SEM images (Figure 2.34), it is evident that the BaTiO3
nanoneedles are of a straight and cylindrical structure, with diameters of about 50

nm and lengths of several nanometres. The growth mechanism is supposed to be

either Ostwald ripening or dissolution-crystallization process, which is clearly
explaining in section 2.8.2.2 iv.
Figure 2.34: SEM images of Ex-situ grown BaTiO3 on anodized plate

X-ray diffraction patterns:
XRD in Figure 2.35 shows that the nano needles are composed of
crystalline, cubic perovskite structure of BaTiO3. The peaks of BaTiO3 [JCPDS
No. 5-0626] 2Ө = 22.5o, 31.9o, 39.2o, 45.72o, 51.3o, 56.58o and 6o.corresponds to
(100), (110), (111), (200), (210), (211) and (220) planes of BaTiO3 respectively
are present which confirms the formation of BaTiO3.
Figure 2.35: XRD of Ex-situ grown BaTiO3
iii. In situ method of preparation of BaTiO3 on anodized Ti plate:

Another method we tried is In-situ growth of BaTiO3 in order to reduce
the effective thickness of dielectric. In this method TiO2 nanotube on Ti plate was
taken as to replace TiO2 nanoparticles. The optimized condition for the growth is

as follows: 10 ml of 0.1M solution of barium hydroxide [Ba(OH)2.8H2O] was

taken in a teflon container. The anodized Ti plate (48 hrs of anodization) was
immersed in it and the Teflon container was sealed and fitted in stainless steel
bomb and heated in a hydrothermal reactor at 120oC for different time points from
3 to 20 hrs.
In this method TiO2 nanotube undergoes dissolution and gets converted to
BaTiO3 in the presence of [Ba(OH)2.8H2O] and gets deposited on the anodized
plate itself. The advantage of this method is instead of BaTiO3 suspension we are
directly obtaining film of BaTiO3 on anodized TiO2. In this method BaTiO3 is
grown at the expense of TiO2 nanotube.
iv. Characterization of Insitu-BaTiO3
SEM:
Figure 2.36 shows the SEM images of insitu grown BaTiO3 on anodized
plate. It is clear that at 3 hrs of growth, BaTiO3 starts to form on TiO2 nanotube.
It seems like scattered nano-needles on TiO2 nanotube but the uniformity of the
film is poor (Figure 2.36(a), (b)). As the growth time increased from 3 to 6 hrs, a
uniform nano-flower structure (Figure 36(a), (c)) was obtained on anodized Ti
plate. When the growth time increased to 20 hrs, a very thick film of (Figure
36(e)) interconnected fibrous structure of BaTiO3 is formed over the plate.

Figure 2.36: SEM images of insitu grown BaTiO3 on anodized plate for (a&b) 3
hrs, (c&d) 6 hrs and (e&f) 20 hrs.
X-ray diffraction patterns:

XRD pattern of 3 hrs (Figure 2.37) growth shows the peaks of BaTiO3
(JCPDS No. 5-0626) and TiO2 (JCPDS No. 21-1272). 2 values of TiO2 are 25o,
38o, 48o, 54o, 63o and the peaks of BaTiO3 was 2= 22.5o, 31.9o, 39.2o, 45.72o.
51.3o, 56.58o and 66.15o.

Figure 2.37: XRD of In-situ grown BaTiO3 for 3 and 20 hrs.
Here XRD shows the pattern of both TiO2 and BaTiO3. As per SEM, the
layer of BaTiO3 is not continuous over nanotube hence peaks of both TiO2 and
BaTiO3 is present. But 20 hrs growth XRD pattern shows the trace of BaTiO3
only. This result infers that BaTiO3 is formed at the expense of TiO2 nanotube and
surface of the plate is completely covered by BaTiO3. The investigation of the
growth mechanism shows that the nano-needles growth can take place via an
Ostwald ripening process. Due to the absence of a stabilizing agent, the spherical
particles undergo aggregation and rupturing and finally start to dissolve due to
higher free energy. At the same time, the TiO2 particles act as a seed to redeposit
the dissolved particles. The crystal starts to grow from the aggregation.
Controlling the growth condition and reaction time can control the crystal growth.
Also the formation of ceramic BaTiO3 nano-needles under hydrothermal
conditions can occur through a "dissolution-crystallization" process. Commercial
TiO2 powders are aggregates of particles having a primary size of 10 to 50 nm.
When they were used as the Ti precursor, the interactions among these small
particles were broken under hydrothermal conditions. When the powders are
dissolved under high temperature, high-pressure, and strongly alkaline conditions,
a variety of hydroxidized Ti-O ion groups are formed. These hydroxidized Ti-O
ion groups are the growth units of BaTiO3 crystallites. When the concentration of
these growth units and Ba2+ reached or surpassed the supersaturation for the

formation of BaTiO3 crystallites, the nucleation of BaTiO3 began and the needles
grew. The following reaction took place in the system:
TiO2 + Ba(OH)2 BaTiO3 (crystallite) + H2O.
In both the methods growth reaction is the same but in Insitu method
mechanism of growth is slightly different, the anodized Ti plate acts as nucleation
sites for growth. Process formation is basically dissolution of TiO2 nanotube, then
reaction with Ba(OH)2 and finally crystallization of BaTiO3 . This entire process
occurs in the proximity of anodized Ti plate, hence the crystallized BaTiO3 gets
deposited on it, whereas in the former case this process occur in the solution
phase hence we obtain a dispersion of BaTiO3. Result of insitu growth is film of
BaTiO3 over anodized plate.
v. Development and characterization of capacitor with Ex situ and In situ
grown BaTiO3:
In-situ BaTiO3 capacitor: The BaTiO3 deposited Ti plates were taken to
study the capacitance. Two Ti plates over which BaTiO3 has grown for 3 hrs were
taken as the electrodes and assembled to form a capacitor. The capacitance is
measured by applying a constant charging and discharging current, figure 2.38(a)
shows the charging and discharging of capacitors with in situ grown BaTiO3 at a
constant external current of 100 µA/cm2 and it shows a capacitance of 62 µF/cm2.
When we assembled a similar capacitor with 20 hrs grown BaTiO3 Ti plates as the
electrode (Figure 2.38(b)), it shows lesser capacitance of 33 µF/cm2 compared to
that of 3 hrs sample. This reduction in capacitance can be explained as: In in-situ
growth mode, BaTiO3 is growing at the expense of TiO2 nanotube; as the time
increases the amount of dissolved TiO2 is greater thus surface area of TiO2
electrode get reduces and also very thick layer of BaTiO3 forms which indirectly
proportional to capacitance which may cause reduction in capacitance. It is
already discussed earlier regarding the role of TiO2 nanotube and why
nanostructuring enhances the capacitance.

Figure 2.38: Charge-discharge of capacitor with in-situ grown BaTiO3 (a) 3 and
(b) 6 hrs at constant current of 100 µA/cm2.
Ex situ BaTiO3 capacitor:

The obtained BaTiO3 is coated on anodized Ti plate (anodized for 48 hrs)
to study the capacitance. The capacitance can be further enhanced by better
control of the coating method.

Figure 2.39: Charge-discharge of capacitor with ex-situ grown BaTiO3 with 48

hrs anodized Ti plate at a constant current of 3 µA/cm2.
From the earlier study with ZrO2 the maximum capacitance is obtained for
48 hrs anodized sample. Here we selected 48 hrs electrochemically anodized Ti
plate as high surface area electrode and Ex-situ prepared BaTiO3 as dielectric and
capacitor is assembled and capacitance is measured. The thickness of dielectric
layer is maintained constant by dropping equal volume of BaTiO3 dispersion over
same area of samples. Figure 2.39 shows the charging and discharging of
capacitors with ex situ grown BaTiO3. The applied charging and discharging
current is 3 µA/cm2 and its voltage variation with time is noted and capacitance is
calculated as per equation 2.9 and found to be 500µF/cm2. From nano-ZrO2 with
anodized Titania show the dependence of capacitance on electrode surface area, as
the electrode surface area increases the capacitance increases. In insitu method of
BaTiO3 growth (where BaTiO3 is grown at the expense of TiO2 ) the electrode
surface area of electrode is utilized for the growth but in ex-situ method
externally prepared BaTiO3 is coated on the high surface area electrode hence it
show higher capacitance of 500 µF/cm2.
Thus, we could develop capacitors with nano-ZrO2 and Nano-BaTiO3 as
dielectric and studied its performance and found that Ex-situ prepared BaTiO3
based capacitor is showing higher capacitance with 48 hrs of anodized electrode.
All these observations show the importance of morphology of electrodes and
dielectric layer. From all the configurations of capacitors, better performance is

shown by 48 hrs anodized Ti/ Ex-Situ prepared BaTiO3/ 48 hrs anodized Ti.
Hence we decided to choose this capacitor to make an integrated module and
study it performance.
2.9. Integration of Ex-situ prepared BaTiO3 capacitor with DSSC
An integrated structure is assembled with Ex-situ prepared BaTiO3 as the
dielectric (as discussed in section 2.8.2.2.v) and its photocharging and discharging
studied. The DSSC is assembled as per section 2.5.3 with eosin dye as sensitizer.
Figure shows the photocharging and it could store voltage upto 0.41 V and its
discharging studied at constant discharging current of 10 µA/cm2 (Figure 2.40).
The discharging shows a sudden decay of voltage followed by slow discharging.
The efficiency of the solar part was found to be very low, i.e. ~1%.
Figure 2.40: Photo charging and forced discharging of an integrated structure

Eosin as the sensitizer in solar cell part and Ex-situ prepared BaTiO3 as dielectric
in capacitor side. The applied discharging current is 10 µA/cm2.
When a 10 µA/cm2 current is applied to discharge, it took around 400 sec

to discharge completely. The rapid voltage decay initially is because of its internal
resistance (IR), similar behavior is observed with ZrO2 dielectric. The IR drop is
the amount of voltage that can’t be converted in the form of useful work. From
the photo charging it is clear that BaTiO3 shows a rapid charging compared to
ZrO2 this may be because of its higher polarizability.

2.10. Conclusion
In conclusion, the first part of this chapter shows the novel integration of a
thin film device combining a PV and a capacitor wherein both are capable of
independent operation as well as combined operation. Succeeding sections details
the device physics of integration like the factors affecting the flow of current from
solar cell to capacitor and the interface between Ti metal and nanostructured TiO2
layer. The optimization of the PV layers and the capacitor layers can further
improve the separate efficiencies of the two components, namely, the generation
efficiency of the PV and the storage efficiency of the capacitor and finally the
integration of better systems of PV and dielectric Capacitor was investigated.
Second part of the study deals with the optimization of a DSSC and
characterization. Even though the focus of this work is basically on the integration
of a storage unit with a DSSC and development of different storage units, little
effort is put to improve the solar part so that the performance of integrated storage
unit can be studied in detail. The role and significance of different layers of DSSC
is also discussed. Final part shows the synthesis of two nano dielectrics; ZrO2 and
BaTiO3 for the development of dielectric capacitor. Even though the energy
density of dielectric capacitor is poor (<0.1 Wh/Kg), it was selected to check the
possibility of storage and we could show that energy generation and storage is
possible. With these studies, it is evident that Integration of a storage unit with a
solar cell is possible but we have to optimize a better storage system to derive
maximum output as useful work. Development of more efficient storage
architectures and their integration with solar PV are described in later chapters. If
the integration scheme can be adequately configured , the integrated device has
the potential to replace conventional PV’s and provide a more cost effective
system that may reduce dependence on external batteries or other storage systems.

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CHAPTER 2

Proof of concept: Upon photo illumination of a dye sensitized solar

Dye (hole) + LiI Dye + Li+ + (1/2)I2

Figure 2.1: Two-electrode sandwich type structure of the carbon incorporated

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The illuminated cell develops a negative photovoltage, which is the

 Independent working as a solar cell and a capacitor is not

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Figure 2.2: Schematic diagrams of 2-electrode phtocapacitor and 3-electrode

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presence or absence of light. Because of its independency this integrated structure

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The DSSC is integrated to capacitor by an external contact, which is

I3- + 2e- 3I – [at electrolyte/counter electrode interface] ------- (2.1)

3I – I3- + 2e- [at dye/electrolyte interface] ------------ (2.2)

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Further, a counter-electrode material of ample catalytic activity becomes

The fill factor and efficiency of DSSC is given as:

ff  Vm * I m  Voc * I sc  -------------------------------------- (2.3)

Efficiency ( )  Voc * Isc * ff  ----------------------------------- (2.4)

Figure 2.4: Schematic diagram of DSSC.

The nanoparticle or nanotubular wide band gap semiconducting materials

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photoelectrons moving through the TiO2 grains in a dye-sensitized nanocrystalline

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2.3. Integration of DSSC with a dielectric capacitor

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The charge workflow in the integrated cell can be briefly explained as

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Generally accepted mechanism for the formation of TiO2 nanotubes are:

1. Field assisted oxidation of Ti metal to form TiO2

2. Field assisted dissolution of Ti metal to form TiO2

3. Chemical dissolution of Ti and TiO2 due to etching by fluoride ions

2H2O O2+ 4H + 4e- ------------------------- (2.5)

Ti + O2 TiO2 -------------------------- (2.6)

TiO2+ 6F- + 4H+ [TiF6]2- + 2H2O ------------------ (2.7)

Ti4+ + 6F- [TiF6]2- ------------------------ (2.8)

The formation of nanotubes in fluoride containing electrolytes is the result of the

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For preparation of DALS another anodization set up is used, in which two

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After anodization, Ti plates were cleaned in distilled water and annealed at

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2.5.3. Assembly of Integrated structure

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200 300 400 500 600 700 800 900

Figure 2.9: UV-Visible absorption spectrum of Eosin gelblich dye.

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Figure 2.11: Practically assembled structure of integrated solar cell with

2.5.4. Device characterization of isolated DSSC

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Charging and discharging of capacitor separately (without the integration) is

Here I is the externally applied charging current to the capacitor, dV/dt is

Figure 2.13: Voltage -Time graph of Ti-TiO2 -ZrO2-TiO2 -Ti capacitor at a

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2.6.1. Physics behind Integration of DSSC with capacitor