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Doctor of Philosophy
Qureshi Mohammad
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Introduction
STATEMENT
I hereby declare that the work embodied in this thesis entitled, “Design & Fabrication of
benzthiazole based white light emitting diodes: Synthesis, spectroscopic and semi
empirical studies” has been carried out by me under the supervision of Dr. S. Sundar
Manoharan.
In keeping with the scientific tradition, whatever work done by others has been utilized,
due acknowledgement has been made.
Department of Chemistry
Indian Institute of Technology Kanpur, INDIA
CERTIFICATE 1
Certified that the work presented in this thesis entitled “Design & Fabrication of benzthiazole based white light emitting diodes:
synthesis, spectroscopic and semi empirical studies” by Mr. Qureshi Mohammad, Department of Chemistry, Indian Institute of
Technology, Kanpur has been carried out under my supervision and has not been submitted elsewhere for a degree.
DEPARTMENT OF CHEMISTRY
INDIAN INSTITUTE OF TECHNOLOGY KANPUR, INDIA
CERTIFICATE II
This is to certify that Mr. Qureshi Mohammad has satisfactorily completed all the courses required for the Ph. D. degree programme.
The courses include:
Mr. Qureshi Mohammad was admitted to the candidacy for Ph.D. degree in 2000 after he successfully completed the written and oral
qualifying examinations.
Head, Convener,
Dept. of Chemistry Departmental Post – Graduate Committee
Department of Chemistry
IIT Kanpur.
Introduction
Acknowledgements
My sincere thanks are due first to my thesis supervisor and Sir, Professor S. Sundar
Manoharan for guiding me in scientific way for the last five years and who taught me that the
worst sin is the lack of aggression, ethics and enthusiasm. I am always thankful to him for
keeping confidence in me while introducing to this challenging field. His valuable suggestions
and positive criticism always kept me on top gear throughout my research stay at IITK.
I would like to take this opportunity to express my gratitude to Drs. Matthias Koeberg,
Jingsong Haung, Donal Bradley, Imperial College, London for helping me in some of the time
decay, time resolved and electroluminescent measurements. I am also grateful to Dr. C. M.
Schneider and Dr. Stefan Cramm, IFF, Juelich, Germany for helping me in XPS and UPS
measurements and their useful discussions. I also thank Dr. Periasamy, TIFR, Mumbai for letting
me use the time decay facilities in his laboratory. I wish to thank Dr. Y. N. Mohapatra and
Samarender Pratap Singh for their help in electroluminescent measurements. Thanks due to Dr.
Asima Pradhan and Sharad Gupta for their help in PL measurements. Thanks due to Mr. Kuntal
Pal for helping me in electro chemical measurements.
Thanks are due to my senior colleagues Dr. Ranjan K Sahu and John Prassana who taught
me basics in the initial stages of my research, to my colleagues, Dr. Manju Lata Rao for her
support and encouragement throughout my stay. Thanks are due to Brajendra Singh, Vimlesh
Chandra, Sonia Arora, Yona Paul, Sreya Dutta, Rishi, Avani, Tanima, Rohit, Karishma, Tapas,
Bijay lakshmi, Chandrani, Kanpriya, Vijayant for their assistance and keeping the lab in good
humor. A special note of thanks to Dr. Roli Saxena and Sonia Arora for helping me in the initial
stages of organic synthesis. Thanks are due to Dr. Chin, Jacob for their help in proof reading of
the thesis.
I wish to thank Sir, Madam Sheeba Manoharan and Himani for keeping a homely
atmosphere and care they took during my stay at IITK.
I am lucky to have friends Srinu, Jyothi, Varam, Sulochana, Sandhya, Rehana without
whom I would not have come to this stage of my career. They all mean a lot to me.
I wish to thank Mr. Uma Shankar and Mr. Nayab Ahmed for their help in collecting
powder X – ray data and NMR data. Thanks due to Glass blowing staff for their cooperation in
making some of the specially designed glass ware.
I wish to thank all my table tennis partners and coaches for letting my academic pressure
off during my practice sessions.
I take pleasure to thank Gopal, Madhaviah, Shikha, Srirammurthy, Bhanu,
Chandrasekhar, Yamuna, Aditi, Anita, Rajesh, Prasanjit, Natarajan, Hari, Shayan, Anil, Bama
Prasad, Neelam, Jhunpa, Peru and all my southern lab, core lab colleagues and friends for their
friendly suggestions and some of the technical discussions.
Finally, I don’t have words to express my profound gratitude to my parents, brothers and
sisters for their support, patience and love.
The financial assistance and facilities provided by the Indian Institute of Technology,
Kanpur, is duly acknowledged.
Qureshi
Introduction
SYNOPSIS
Thesis Title: Design & fabrication of benzthiazole based white light
empirical studies
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Introduction
CHAPTER II deals with the aspects of synthesis and characterization techniques. A host
of benzthiazoles, oxazoles and imidazoles prepared either using microwave or by wet
method is described and tabulated. The advantages of microwave synthesis over wet
route are highlighted. The structural characterization of these molecules synthesized has
been carried out using NMR, IR, Elemental Analysis and thermo gravimetric techniques.
Reduction – Oxidation behavior of these molecules were evaluated employing cyclic
voltamograms. Absorption and emission spectra were studied in both solid and solution
form to understand the features of electronic transitions. Fluorescence decay
measurements using Time Correlated Single Photon Counting (TCSPC) spectroscopy
were carried out employing N2 pico second pulsed laser. Time resolved spectral studies
were done using ultra fast response CCD camera. Photo generated time – of – flight
(TOF) electron mobility measurements were carried out using frequency tripled Nd:
YAG laser with incident power ~ 5mJ/cm2. We highlighted the use of Ultraviolet
photoemission spectroscopy (UPS) and X – ray photoemission spectroscopy (XPS)
studies to understand the interfacial energy level alignments in organic hetero junctions
and valence band spectra for the electronic structures of the molecules.
CHAPTER III deals with the stereo selective white light emission among the 1,2 –
dibenzthiazolyl ethylene isomers. The cis - form of the isomer distinguishes itself from
the trans - form in showing white light emission, where as the trans form shows a single
component emission in the green wavelength region. Time decay measurements of both
the isomers were studied. In the solid-state, the cis form of the isomer shows a faster
Introduction
decay in comparison to the trans isomer indicating an extended energy transfer between
the benzthiazolate chromophoric groups. Nano second time resolved spectral studies
shows a strong time dependency during the first few nano seconds (1 – 6 ns) in the case
of cis isomer leading to a red - shifted emission where as no time dependency was
observed in the case of the trans isomer. This suggests a distinct energy transfer
processes operating in the cis form of the isomer. Energy minimized structure suggests an
angle of 400 around the –C=C-C=N where as trans isomer is coplanar with an angle of
~ 1740. AM1 – CI calculations suggest electron density distribution showing a strong
energy transfer from the adjacent benzthiazolato groups in the cis isomer through the
olefinic linkage with a predominant ‘space charge transfer’ in the second excited state,
LUMO +1. On the other hand, for the trans isomer there is no change in the distribution
in the electron density. In the device structure such as ITO/PEDOT: PSS/PFO: CDBE
(10%) /Al, the cis - form of the isomer, which shows white light emission was employed
as an emissive layer. It is noteworthy that the electroluminescent spectrum of this device
shows a broad white light emission similar to the PL spectra of the cis – DBE that
confirms that the generation of excitonic zone is in the cis – DBE that is responsible for
the white light emission. The threshold voltage of the device structure is at 8 V with an
initial brightness of 30 cd/m2.
CONTENTS
Acknowledgements ---- V
SYNOPSIS ---- VII
CONTENTS ---- XI
properties, and such a flexibility in tuning its properties is one of the principal reasons for
molecules and polymers have pronounced optical qualities that can be adjusted by
and polymer chains may be enhanced by delocalized electrons from sp2 hybridized
carbon atoms, the intermolecular overlap of van der Waals bonded solids generally limits
charge transport mobilities, 10 cm2 /Vs at room temperature; increasing to ~ 105 cm2/Vs
at low temperature. Thus, the transport characteristics of organic films are strongly
dependent on the molecular order. To avoid the need for very large voltages, organic
devices should employ thin films of molecules designed for optimum molecular overlap.
Most of the initial studies on the solid-state properties of these materials concentrated on
the molecular crystals because ordered crystals possess better electronic transport
under steady-state bias was made by Helfrich and Schneider using anthracene. The
applied potential was over 100 V for the onset of EL since used crystals of several
microns thick, thereby limiting the possible practical applications of this technology.
polycrystalline anthracene thin films. The ability to make much thinner devices using this
technique significantly reduced the voltage required to generate light. However, in these
2
early devices, electron-hole combination occurred very close to an injecting contact and
The process of light emission in organic light emitting diodes is based on the injection of
positive and negative carriers from electrodes that sandwich an organic layer. These
recombine to form excitons that can radiatively decay to produce electro luminescence
from the device. The emission color can be tuned over a wide range by appropriate
choice of polymer and small molecule based organic materials. The basic structure of
the organic light emitting diodes is shown in figure I.1. Electrons injection from the
cathode is from a low work function material and hole injection is facilitated by the Hole
transport layers. The device is placed on an ITO substrate that is transparent and
ITO-Glass substrate
Figure I.1 : Typical device architecture of an Organic Light Emitting Diode consisting of hole transport and
electron transport layers for the ideal recombination of electrons and holes.
3
In order to understand and therefore, maximize the efficiency of an OLED, we
need to consider the various loss mechanisms. Figure I.2 shows the schematic of the
processes involved in EL devices. The charge carriers recombine in the organic layer to
produce excitons. The first loss process occur due to carriers that do not combine, the
probability of which is related to the balance between the number of positive and
negative charges injected into the organic layer. The excitons that are formed can be of
two types, singlets that have a radiative decay and triplets that decay through non -
radiative processes and thus lead to a loss in efficiency. All the singlet excitons do not all
radiatively decay, due to the presence of non - radiative pathways for the excitonic states
the organic materials as well as the additional losses due to the exciton quenching
mechanism. Finally, a large portion of the light generated in the device is unable to
These four major losses described above can be combined to determine the external
4
h e
h–e
Singlet Triplet
exciton Exciton
Emission
Thermal
deactivation
Radiationless
deactivation
External Internal
emission reflection loss
Figure I. 2: Schematic diagram for the electro luminescent processes describing various
loss mechanisms involved in controlling the efficiency of the emission process
5
I. 3: Amorphous and polycrystalline organic devices:
A significant step forward in organic technology came with the publication by Tang and
vanslyke of solar cells and light-emitting devices fabricated from thin amorphous and
disordered films possess inferior electron transport characteristics, they can satisfy the
Mg:Ag O
N N
Alq3 Al N
Diamine O
O
ITO
Glass N
Alq3 S
Diamine
N N
N N
TPD α- NPD
Fig. I.3: Tang and van Slyke’s (1987) organic light emitting device is built on a glass
substrate coated with a transparent indium tin oxide layer acting as the anode. A
diammine was used as the hole transporting material since this class of materials was
found to have stable conductivity properties in earlier work on photoconductors. Many
variations on the basic diamine structure were later investigated; for example, both
TPD and -NPD were found to make successful hole transport layers. The electron
transporting and luminescent material employed was Alq3. In this hetero - structure
devices electrons and holes combine at the diamine/Alq3 interface, but whereas there
is minimal electron injection into the diamine layer, some holes penetrate into the first
100Å of Alq3. Thus, excitons are formed in the Alq3 and emission is observed from
Alq3 fluorescence. Electrons are injected into the organic layers from an Mg: Ag alloy
cathode with an additional layer of Ag to protect the Mg from oxidation.
6
Indeed, thermal evaporation is capable of growing continuous, molecularly -
smooth, films as thin as 100Å, allowing vertical device feature sizes approaching
molecular scales.
~1000Å in the solar cells and light-emitting devices enabled a dramatic reduction in
operating voltage. A significant step was to use amorphous films to fabricate the first
organic hetero - structure light emitting device, increasing the quantum efficiency of
of less than 10V; the hetero - structure design was also used in a 1% power efficient solar
cell. With this work, organic materials first showed their potential as the basis for an
efficient emissive technology applicable to all aspects of the display industry. An intense
7
I. 4: Polymeric light-emitting devices:
using small molecular weight materials, attention turned to the development of polymeric
electro luminescence. Polymers are too large to be thermally evaporated, so unlike small
molecules they are often cast from solution by spin coating technique, complicating the
EF
Electrons
(a)
E
Hole
s
F
ITO
PPV Ca
EF
Hole Electrons
(b)
Holes
EF
ITO PPV
PBD Ca
Figure I.5: Proposed energy structures for the single layer and hetero – structure PPV
devices. In (a) the electrons and holes combine close to the calcium electrode reducing the
quantum efficiency. However, in the hetero – structure device shown in (b), the holes are
trapped at the PPV/PBD interface and the overall quantum efficiency is nearly two orders
of magnitude higher. After Brown et al (1992).
8
However, a widespread interest in polymer chemistry and the belief that polymer
structures were more structurally robust spurred the development of the first polymer
electro luminescent device. The material used was poly (p - phenylene vinylene) (PPV),
which is fluorescent in the yellow-green. Partly due to lack of a hetero structure, the
initial polymer device possessed a quantum efficiency of only 0.05%, similar to the
thermally deposited anthracene electro luminescent devices that predated the hetero
Since PPV preferentially conduct holes, the original devices constructed from
films of PPV were limited by electron injection. This deficiency was addressed the by a
polymeric hetero structure using an electron transport layer of the molecular material 2-
polymer, poly (methyl methacrylate) (PMMA). This improved the quantum efficiency of
PPV electro luminescence to 0.8%, roughly the same as the undoped Alq3 devices.
efficiency using hetero structure. For example, the range of substrates was expanded to
include flexible plastic and new luminescent dyes were introduced to improve the device
performance across the visible spectrum. One aspect of the organic technology that
remained unrealized, however, was the potential for highly transparent devices.
9
Figure I. 6: The device structure of the metal-free transparent organic light-emitting
device together with its transmission spectra. A thin layer of CuPc underneath the
top ITO cathode protects the remaining organic layers from damage during the ITO
sputtering process. Subsequently, it was discovered that materials with lower optical
absorption than CuPc had similar protective qualities, while improving the optical
transmission of the device. From Parthasarthy et al (1998).
Semitransparent devices had been developed earlier using very thin metal contacts
[2] but the metal-free device [3] of Parthasarathy et al. shown in Fig. I.6 employed a
protective layer of CuPc and a sputtered film of indium tin oxide. Not only did the device
have important technological implications, it also demonstrated that the electron injection
luminescence in the initial papers; the commercial development of this technology was
retarded by reliability problems. The organic materials are sensitive to both oxygen and
water, and maintaining the devices in an inert atmosphere is critical to their long-term
commercially acceptable lifetimes of ~ 10,000 hours were ultimately realized and several
10
prototype full-color organic displays have now been demonstrated. One such display is
shown below in Fig.I.7, fabricated on a poly silicon thin film transistor back plane. Note
that the organic emissive devices are Lambertian emitters and therefore the color is
relatively independent of viewing angle. This further facilitates note the very thin and flat
display.
Figure I.7: 15” - Organic active matrix displays, Eastman Kodak Company and Sanyo
Electric Co. This material used molecular organic materials for producing full color
emission
light emitting devices (OLEDs). Brightly emissive across the visible spectrum, organic
materials are readily incorporated in electrical devices that are inexpensive to fabricate on
a large scale. Organic devices may be grown on glass or flexible transparent plastic and
they can operate below 10V. Due to these advantages, it is envisaged that OLEDs may
provide the platform for the next generation of video displays. But organic materials must
not only match the color purity and long-term stability of competing technologies, they
must also possess a significant advantage in efficiency, especially in low power, portable
applications.
11
I. 7: White light emission, a simple way to achieve full color emission:
Owing to the difficulty in controlling the electronics for three different pixels [4] in
achieving full color display, research is now directed towards the simple device
fabrication methods, which can reduce the complication in the device making. One of the
major set backs in the commercialization is the lifetime of the devices in particular
concerning the blue light emitting materials. Larger bandgap materials often pose the
problems of getting degraded near the cathodic surfaces, which is of concern to the
industry [5]. A variety of strategies have been developed to make white LED, in most
cases by combining several emitting species of different colors [6]. However, multi layer
devices fabricated by vapor deposition are not only difficult to assemble, but also require
suitable blockers at the interfaces to control the flow of electrons. Blending several
dyes/polymers together faced other kinds of complexities, such as color instability due to
voltage changes and / or undesired Fröster – type energy transfers among chromophores
[7]. Most of these problems can be avoided if single component material can be used as
emitting species. Several approaches to achieve full color displays are shown pictorially
in figure I.8. Achieving full color emission based on the white light emission seems to be
more practical because of the availability of established cheaper filter technology; also
electronics part considerably. One of the primary requisite to obtain white light emission
12
0.33, 0.33
I. 8: Can white light emission be possible with the steric control of the organic
molecules:
molecular structure, then they do not interact in the ground state and practically the –
electronic absorption spectrum is equivalent to the sum of the absorption spectra of the
separated entities [8]. For example, the absorption spectra of the 1- naphtyl – 9 anthryl
alkanes, are very similar to that of an equi - molar mixture of 1-methyl naphthalene and 9
13
CH2 n
If the steric conformation of the molecular chain is such that the excited segment
cannot approach a second unexcited segment, then the excited species emits characteristic
spectrum. On the other hand, if during the lifetime of the excited species it can move into
would give a structureless fluorescence spectrum at lower energies than the molecular
spectrum. This typical behavior has been observed in the diphenyl alkanes, the triphenyl
CH2
n
14
I. 9: Brief literature review on the molecular organic electro luminescent materials:
One of the key enablers in the history of OLED advancement can be attributed to
the continuing discovery of new and improved electro luminescent materials, which were
made possible by the dedication, and ingenuity of many organic chemists who provide
the design and skilled synthesis. Indeed, from small molecules, oligomers to conjugated
polymers; intense research in both academia and industry has yielded OLEDs with
treatment can reduce the carrier injection energy barrier, remove residual organic
contaminants and get its work function up to near 5eV which is still about 0.5 eV lower
than most of the HOMO of the hole – transport materials. A layer of hole – injection
material, which reduces the energy barrier in between ITO/HTL, is therefore beneficial to
enhancing charge injection at the interfaces and ultimately improving power efficiency of
the device. Thus, hole – injection can be promoted by introduction of new hole –
transport layers with optimized HOMO levels and by inserting a thin layer of copper
phthalocyanine (CuPc) [11], starburst polyamines [12], polyaniline [13] and SiO2 [14]
between the ITO/HTL interface. In addition, HTLs doped with oxidizing agents such as
FeCl3 [15], iodine [16], tetra (flouro) – tetra (cyano) quinodimethane (TF – TCNQ) [17]
reported as an effective material for hole – injection. One of the widely used polymers for
15
as PEDOT/PSS which has been found to be useful in a hybrid OLED architecture
combining both the advantages of polymer LED (PLED) and multi – layered small
molecule OLED [19]. One of the potential drawbacks of using PEDOT/PSS is its acidity
which could get as high pH as ~ 3. Nuesch et al. [20] found that the surface treatment
using grafting of molecule and adsorption of acids or bases [21] on ITO could also
modify its work function. In case of 2 – chloroethyl phosphoric acid, a self – assembled
mono layer (SAM) can be readily formed on the ITO substrate, which significantly
materials such as SbCl5 – doped N, N′-bis (m- tolyl) – 1,1′ – biphenyl –4, 4 – diamine
(TPD) thin film [23] as well as the amorphous starburst amine, 4,4′, 4′′ – tris (N, N′-
diphenyl amino) triphenylamine (TDPTA) doped with a very strong acceptor TF – TCNQ
+
SO3 H
O O
H3C
n
SbCl-6
S m
N N
PEDOT/PSS
CH3 R'
s s s
TPD R'
s s s
R'
– 6T R'
16
The discovery of using tri – aryl amines with a “bi-phenyl” center core as the hole
– transport layer which greatly improved both EL efficiency and operational stability of
OLED [25], led to most of the new hole transport materials (HTM). The creativity of
synthetic chemists as well as material scientists throughout the world continue to provide
the OLED device community with their ever improved products having superb properties
and elegant design. By far, one of the most widely used HTM in OLED is still N, N′ - bis
Therefore, studies on the design and synthesis of new HTMs have been continually
focused on finding materials with high thermal and thin film morphological stabilities
and on finding ways to control and optimize carrier injection and transport. These
Heat treatment of organic multi – layers has been found to cause an inter - diffusion
between organic layers in OLED [26] which ultimately affects the stability of the device.
display. Using thermo dynamical consideration, Sato has proposed a molecular design
rule according to which high Tg materials can be obtained by increasing the number of
– electrons and by decreasing rotational moment by placing a heavy moiety at the center
17
CH3
N N
S
N N
H3C
TTBND BFA – I T
To date, the most widely used electron – transport and host material in OLEDs is still tris
morphologically stable to be evaporated into thin films, easily synthesized and purified.
Arguably, it is still one of the most robust electron – transport backing layers in OLED,
particularly with the help of the hole blocker to trap the hole carriers from injecting into
Alq3 [28] or doping with lithium or other alkali metals [29] to assist electron injection to
lower the drive voltage [30]. But it has also many shortcomings such as quantum
efficiency, mobility, band gap and the ashing problem during sublimation. It has been
found by the time – of – flight technique that the drift mobility of electrons in Alq3 is
increased by about two orders of magnitude (10-4cm2/Vs) as the deposition rate decreased
from 0.7 to 0.2 nm/s. The electron drift mobility in Alq3 is found to increase linearly
with the square root of the applied electric field. Other metal chelates which showed
decent device performances and interesting fluorescent properties are shown below.
Sano et al from Sanyo [31] have prepared several kinds of 2:1 complexes with 8 –
18
hydroxyquinoline derivatives and a variety of metal ions, such as Be, Mg, Ca, Sr, Sc, Y,
Cu or Zn. Amongst them, the beryllium complex was found to be the most fluorescent in
the green and Zinc complex was found to have a strong yellow fluorescence. Some of the
metal complexes are shown below. One of the most widely used electron – transport and
oxadiazole (PBD) which has been branched, spiro – linked [32] and starburst to prevent
electron – withdrawing and bulky dimesityl boryl groups [33,34] one could produce a
Current glassy and amorphous organic molecular materials have low – electron
are usually more chemically sensitive to their environments, hence, very few useful
O N
O
N N O
O B
N O
Zn
N
N
Al N
N O N
O
O
N N
O
Ph2Bq
Al (ODZ) 3 Zn(BIZ)2
N
O N N N
O
O
Be Be
Zn
O O
N O
N N N
19
Oxidiazole containing organic materials generally possess good electron – transport
transport materials in OLEDS [35-38]. Two soluble tris (phenyl) quinoxalines have been
identified in the literature as the effective electron – transport materials, which are tris
yl] benzene (TRQ1) and 1,3,5 – tris [{3- (4 – tert – butyl phenyl) – 6 – trifluro methyl} –
quinoxaline – 2 yl] benzene (TRQ2) [39]. The electron mobilities for both compounds
approach 10–4cm2/Vs at electric fields of 106 V/cm at room temperature. The electron
in the range of 3.9 x 10-4cm2/Vs at 2 X 105 V/cm to 5.2 x 10-4 cm2/Vs at 2x 105 V/cm
with a weak dependence on the electric field [40]. Although the electron mobilities in
those materials are one or two orders magnitude greater than that of Alq3, only a few
experiments have been carried out to replace Alq3 with the new materials in OLEDs.
I. 12: Anode:
the energy difference between the electrode work function and the ionization potential of
the organic material. This is generally a very poor approximation and has been shown to
experiments on some new hole – transport materials showed that with OLEDs on ITO
glass the device turn – on voltage and quantum efficiency were not correlated well with
the ionization potential of the hole – transport materials, indicating that injection of
carriers cannot be fully controlled by simply varying the energy offset barrier at the
electrode.
20
I.12a: Surface treatments of ITO:
at its surface. The work function shift induced by a uniform dipolar surface layer is
determined by the change in electrostatic potential ( V) created at the surface and can be
surface number density, r the dielectric constant of the polar adsorbate molecules, and
µ mol is the molecular dipole normal to the surface [41]. There are few important ways one
can efficiently do the surface treatment of ITO, namely (i) acid – base treatments, [42],
Over the past few years, increasing activity has focused on improving charge
materials have been explored as alternatives to ITO as OLED anodes. ITO has the virtue
materials have been recently examined as anode, however all suffer from some
unfavorable characteristics. For example, Fluorine – doped tin oxide, germanium based
I.14: Cathode:
Elemental metals with low work functions are ideally suited for the use in OLED
as the cathodes, since, having a low they can inject electrons easily. Stossel et al [46]
–9
have investigated the Alq3 – base OLEDs prepared at 5 x 10 mbar with the cathode
work function ranging from 2.63 to 4.70 eV. They have showed that lower the work
function of the metal higher is the current density obtained in the device structure. The
21
attempt to use Ca, K, and Li for effective cathode materials revealed that they exhibit
poor corrosion resistance and high chemical reactivity with the organic medium. Thus, a
variety of low work function metal alloys such as Mg – Ag and Al – Li are used for
cathodes. [47]
color, and most importantly stability. There has been extensive research efforts aimed at
majority of these reliability studies concerned OLEDs employing the common electron –
transport material, Alq3. The operational instability is a long – term intrinsic decay in EL
intensity leading to a uniform loss of efficiency over the device emitting area. The
storage instability occurs through the formation and growth of non-emissive regions or
“dark spots”
One of the main issues concerning small molecules is the crystallization owing to
their low molecular weights. Since organic thin films prepared by vapor evaporation are
especially those used for HTL, have relatively low glass transition temperatures (Tg). For
example, while using TPD as a hole transport layer, light output gradually decreased with
increase in temperature and dramatically dropped at 700C, which corresponds well to the
glass transition temperature, Tg ~ 600C [48]. As a result, many methods have been
22
problem. Molecular dopants were also proven to suppress crystallization, along with
Apart from the above mentioned problems, operational stability due to unstable
anodic contacts [49], excited state reactions [50], self – heating during operation [51],
presence of non – emissive sites [52] and reaction of cathodes with moisture [53] will be
Inspite of good efficiencies and light output, there are very few reports available
in the literature on benzthiazole-based compounds. The main reason being the lack of
understanding about the photo – physics and physics involved at the interface of the
organic devices. Some of the literature reports wherein use of benzthiazole materials as
1. First report on the white light emission based on benzthiazole moieties was by
Hamada et al where in they have shown white light emission based on single
2. Lim et al [55] reported white light emission and bis [2-(2-hydroxy phenyl)
pyran (DCM2) dye based on the partial energy transfer from dye to the Zinc
23
3. Zhang et al demonstrated a benzthiazole based blue light emitting diodes in the
on the proton transfer kinetics were studied by P.F. Barbara et al [57] and Ding et
al. [58].
derivatives where in they demonstrated the energy transfer from the benzthiazole
lumophoric groups have been subject of recent interest because of the high
common active groups. Further more there are few reports by Hamada et al on
White light emitting materials holds promise as candidates for full color
display technology by virtue of its flexibility and stability. Understanding the photo
improve the approaches to device fabrication. Exploring new materials, which will
24
give white light emission in diode environments, forms the basis for the present
work. In this context understanding the photo and device physics involved in
benzthiazole based molecular materials is the main focus of the presented work.
visible region.
molecules.
complexes
25
I.17: References:
1. C.W. Tang, S.A. Vanslyke, Appl. Phys. Lett. 51, 913, 1987; C. W. Tang, US
4. G.Gu, G. Parthasarathy, P. Tian, P.E. Burrows, and S.R. Forrest, J. Appl. Phys.
6. M. Granstroem and O. Inganas, Appl. Phys. Lett. 68, 147, 1996; M.Berggren,
Nature (London) 372, 444, 1994; F.Hide, P. Kozodo, S. P. DenBaars, and A.J.
7. J. Kido, M.Kimura, and K.Nagai, Science 267, 1332, 1995; J.Kido, M. Kimura
and K.Nagai, Appl. Phys. Lett. 67, 2281, 1995; S.Tasch, E.J. W. List, O.
Scherf, and K.Muellen, Appl. Phys. Lett. 71, 2883, 1997; C. –I. Chao and S.-A.
Chen, Appl. Phys. Lett 73, 426, 1998; A. –A. Chen and C. –I.Chao, Synth. Met.
79, 93, 1996; T.-W. Lee, O.O. Park, H.N. Cho, J.-M.Hong, C.Y.Kim and
Y.C.Kim, Synth. Met.122, 437, 2001; J. P. Yang, Y.D. Jin, P.L. Heremans, R.
26
8. O. Schnepp and M.Levy, J. Am. Chem.Soc, 84, 172, 1962.
10. I. –M. Chan, W. -C. Cheng, F. C. Hong, Asia Display/IDW’01, 1483, 2001.
11. S.A. Vanslyke, C.H. Chen, C.W. Tang, Appl. Phys. Lett. 69, 2160, 1996.
12. Y. Shirota, Y.Kuwabara, H. Inada, Appl. Phys. Lett 65, 807, 1994.
13. Y.Yang, A.J. Heeger, Appl. Phys. Lett 64, 1245, 1994, Y.Cao, G.Yu, C. Zhang,
14. Z.B.Deng, X.M.Ding, S.T.Lee, W. A. Gambling, Appl. Phys. Lett. 74, 2227,
1999.
15. D.B. Romero, M. Schaer, L.Zuppiroli, B. Cesar, B.Francois, Appl. Phys. Lett, 67,
1659, 1995.
17. J. Blochwitz, M.Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett. 73, 729, 1998.
18. A.Yamamori, C. Adachi, T. Koyama, Y. Taniguchi, Appl. Phys. Lett. 72, 2147,
1998.
20. F. Nuesch, F. Rotzinger, L. Si-Ahmed, L. Zupioli, Chem. Phys. Lett. 288, 861,
1998.
21. F. Nuesch, E.W.Forsythe, Q.T.Le, Y.Gao, L.J.Rothberg, J. Appl. Phys. 87, 7973,
2000.
22. S.F.J. Appleyard, S.R.Day, R.D. Pickford, M.R. Willis, Opt. Mater. 9, 120, 1998.
27
24. X. Zhou, M. Pfeiffer, J. Blochwitz, A. Werner, A. Nollau, T. Fritz, K.Leo, Appl.
40, 1998.
27. Y. Shirota, Y.Kuwabara, H. Inada, Appl. Phys. Lett. 65, 807, 1994.
28. Y. Hamada, N. Matsusue, H. Kanno, H. Fujii, Jpn. J. Appl. Phys. 40, L753, 2001.
30. Z. Liu, J. Pinto, J. Soares, E. Pereiara, Synth. Met. 122, 177, 2001.
35. H. Tokuhisa, M.Era, T. Tsutsui, S. Saito, Appl. Phys. Lett. 66, 3433, 1995.
1999.
28
41. P.A. Cox, The Electronic Structure & Chemistry of Solid, Oxford university
42. F. Nuesch, L.J. Rothberg, E. W. Forsythe, Q.T. Le. Y. Gao, Appl. Phys. Lett. 74,
43. C. C. Wu, C. I. Wu, J.C. Strurm, A. Kahn, Appl. Phys. Lett. 70, 1348, 1997.
44. M. Mizno, T. Miyamoto, Jpn. J. Appl. Phys. 39, 1849, 2000; A. Anderson, N.
1998.
Schlaf, Z.H. Kafafi, D.B. Chrisey, Appl. Phys. Lett. 76, 259, 2000; H. Kim, A.
Solid Films, 377, 798, 2000; J. Zhao, S. Xie, S. Han, Z. Yang, L. Ye, T. Yang,
111 ,19,2000.
47. C. W. Tang, S.A. Vanslyke, C.H. Chen, J. Appl. Phys. 65, 3610, 1989.
48. S. Tokito, H. Tananka, K. Noda, A. Okada, Y. Tga, Appl. Phys. Lett. 70, 1929,
1997.
29
50. Z. D. Popovis, S. Xie, N. –X. Hu, A. M. Hor, D. Fork, G. Anderson, C. Tripp,
Taniguchi, C. D. Merritt, H. Murata, Z.H. Kafafi, Appl. Phys. Lett. 75, 766, 1999.
52. P. E. Burrows, V. Bulovic, S.R. Forrest, L.S. Sapochak, D.M. McCarty, M.E.
Sheats, R.L. Moon, J. Appl. Phys. 80, 6002, 1996; H. Aziz, Z. D. Popovict, S.
Xie, A. –M. Hor, N. –X. Hu, C. Tripp, G.Xu, Appl. Phys. Lett. 72, 756, 1998; H.
Aziz, Z. D. Popovict, C. Tripp, N. –X. Hu, S. Xie, A. –M. Hor, G.Xu, Appl. Phys.
Lett. 72, 2642, 1998; Y. F. Liew, H. Aziz, N. -X. Hu, S. –O, Chan, G. Xu, Z. D.
54. Yuji Hamada, Takeshi Sano, Hiroyuki Fujii, Yoshitaka Nishio, Hisakazu
Takahashi and Kenichi Shibata, Jpn. J. Appl. Phys. 35, L1339, 1996.
55. J. T. Lim, N.H. Lee, Y.J. Ahn, G.W. Kang and C.H.Lee, Current Appl. Phys. 2,
295, 2002.
56. X. H. Zhang, O.Y. Wong, Z.Q. Gao, C.S.Lee, H.L. Kwong, S.T. Lee and S.K.
57. P.F.Barbara, L.E.Brus and P.M. Rentzepis, J. Amer. Chem.Soc.,102, 5631, 1980.
58. K.Ding, S.J. Courtney, A.J. Stranjord, S.Flom, D.Friedrich and P.F. Barbara,
30
59. Takashi Sasaki, Takashi Inoue, Yukari Komori, Satoshi Irie, Kensuke Sakurai and
66. Beniot Domerq, Caro Gresso, Jose – Luis Maldonado, Marcus Halik, Stephan
Barlow, Seth R. Mardes and Bernard Kippelen, J. Phys. Chem B, 108, 5147,
2004.
67. Q. Lin, C.Y. Shi, Y.J. Liang, Y.X.Zheng, S.B. Wang and H.J. Zhang, Synthetic
68. Kexhi Wang, Ling Huang, Lihua Gao, Chunhui Haung and Linpei Jin, Solid State
69. J.-K.Lee, D.S.Yoo, E.S.Handy and M.F.Rubner, Appl. Phys. Lett.69, 1686, 1996.
31
75. X.T.Tao, S.Miyata, H.Sasabe, G.J.Zhang, T.Wada, M.H.Jiang, Appl. Phys.Lett.
78, 279,2001.
Lett.77,3272,2000.
2000.
Conference on EL Mol. Mater. Relat. Phenom. (ICEL – 3), O – 29, Los Angelo’s,
32
33
!
π " π# " π#
% !
&" '
))*
* +
.
,- . / ,0 .
&1 / 2 &
34
" " # $""# %
3 ) '""# (
4 5
% 6 7 ,.
NH2
+ R - COOH
SH
I II
N
R
S
35
I
II
+
/ $ 2 ,,/%& 2 &'
0 & , &
1 0 0
/ '
' / (
' (
36
'&1- . ! 8 (
))*
& 1- + 8 9 .. : *
3 1!
7 ,- / &.
&1 / 2 & 7
; 8 1< 8
))* *
37
NH2
R - COOH +
XH
O O
+
O P O +P O
O- O-
NH3+PPA- O O O
+ +
+ R C O O P O P O
XH O- O-
N
R
X
( )$ 4- 5 %
! & /
))*
% (6 ,.
=.#
38
%# )
; 8 1< 8
))*
5 )
OH
NH 2 COOH
+
SH
I II
HO
N
( & '&5 / (
,
/ &' & . , /& . 6 7 ,8
0 & & , 6 7( 8
1
H NMR (CDCl3) δ 7.2351, 7.3632 (q, J = 6.84Hz), 6.9312 (td, J = 7.8 Hz, 8.56 Hz), 7.0838 (d, J
= 8.2 Hz), 7.6567 (d, J = 7.84 Hz), 7.8569 (d, J = 8.04 Hz), 7.9539 (d, J = 8.04Hz). IR, (KBr,
,2 .. ,9
2 - & -
$ & /
))* &.@ 9 .. :
,. 3 2! 1.@
; 8 1< 8
))*
A - & -
& /
))* ,- - 1@
40
;
NH 2
SH
I II
HOOC
HOOC COOH
COOH
N N N
S
S S
S
N
cis – 1,2 – dibenzthiazolyl ethylene - 1H NMR (DMSO – d6) δ 7.2473 (1H, d, J = 12.4
Hz), 7.9868 (1H, d, J = 7.6Hz), 7.8093 (1H, d, J = 8.04Hz), 7.3504 (1H, t, J = 3.9Hz),
7.456 (1H, t, J = 3.94Hz). IR (KBr; ν/cm-1) 1513, 1435, 937, 758, 647; Elemental
16.98 Hz), 7.8312 (1H, d, J=8.28 Hz), 7.7501 (1H, d, J = 8.28 Hz), 7.5017 (1H, t, J = 8
.84 Hz), 7.4377 (1H, t, J = 9.0 Hz), IR (KBr, ν/cm-1) 1510, 1429, 920, 745, 667;
Elemental Analysis: %C: 65.12, %H: 3.1; %N: 9.32; %S: 21.80.
41
+ &2 -
$ & - /
& /
3 +! B ))*
&.@ 9 .. :
,& *
; 8 1< 8
,- .
.
7 ,..
.
,9 . ,- C 9 .@
42
NH2
+
HOOC COOH
SH S
I II
N N
S S S
+ $ & - /
/ & + ,,/& . ' &6
. ,8
0 & & , 6 . (8
1
H NMR (CDCl3) – δ 7.5243 (t, J=4.06 Hz), 7.6035 (t, J=3.96 Hz), 8.0869 (d, J
13
=4.99Hz), 8.187 (d, J=4.95 Hz), 7.974 (s), C – NMR: δ 160.33, 153.855, 140.297,
$ & - "
& /
43
,...
- &... D2
C =- @
COOH
NH2 HO
+
SH OH
COOH
HO
N S
S N
OH
44
)
: 'H I νJ ",
( / =.- 0 =& ,- 0 = 2 9 ,1&D ,D ,=.2 D- 0 ,1 0 1
2 0 D &1 D0 = .0
: : " 6
$; < &= &' 9 %
/
0
NH2 OH HO 7 ,$( . % 7 $ ,%
HOOC N
XH
+ 2 $( . % 1 2 $ ,%
X
* ,$( . % . . $ ,%
45
HOOC N 7 ,$ 2 %
)
X
COOH X
( ,$ 2 %
N
. ,$ 2 %
)))) 7 $ ,%
HOOC COOH X N
N X
1 2 $ ,%
. . $ ,%
N N * ,$( . % 7 ,$ ,%
HOOC COOH
S X S X
* 2 $( . % ( 2 $ ,%
* ( $( . % 7 $ ,%
X N
+ . $* %
OH
OH
COOH
* ,$* %
. /
! F$+: ' (
, ,=
8 ;!7 ;!7 F <K
F; ! K !$ 7
I 4 && 3 7
K ,,.9
46
,.. / &..
'&- 1 =1- (
. /
& / & - /
& - /
$ E! 3
4 5
7 " -/ >
>
',( ; ! 7 7
47
'&( + * ' +*( E $
'E $ (
'=( ' 4(
'1( B 4 / 4 $
'- ( ' $) (
'D(
'0 ( L / ) $ 'L )$ (
',.(
' +*(
+*
"
"
. , µ +*
+*
48
+*
7 ? / $? /%
7 / @
49
*
)7 ; < ; / ,...
3 * J*
'E ! 3 (
$ ) ' $) (
"
$ )
50
) :
M,5
M 5 MI 5
A .
/ /
'8 &9 .0 (
=,- )K
51
1... / - ...J 'N . - @ (
- / ,. ,. =J
" J
> K $*3 *
. ,OF 1=. - 8
52
1.06 532 nm SPCD BS M
CW,ML,
KTP
M DYE OSC
R
UV SAC
M
S VISIBLE
C SHG
M
DELAY
PMT CFD
ST
S ST
M A
TA BA MCA
PDP 11/03
M
CFD RM
PM Cyber
170
+<
+< "
0. "
53
E
E . - ,D
,D &
7 - -A >
/ "
/ ; > C* + λ G =- -
'λ τ G D & 8 (
"&
) N - F B
3A 7! *
Sample
Metal electrode
Bias Voltage
Figure II. 9: Block diagram of photo generated Time – of – Flight technique used.
54
K
: τ ', N
& µ (
7 D $D " % ; - $; " %
L )$
' (
I B )$
'
55
> "
ν → A+ + e-
A + hν ------------------------- (2)
The final term in brackets, representing the difference in energy between the ionized and
neutral atoms is generally called the binding energy (BE) of the electron - this then leads
ν - BE
KE = hν ------------------------- (5)
1. A source of fixed-energy radiation (an x-ray source for XPS or, typically, a He discharge lamp for UPS).
2. An electron energy analyzer (which can disperse the emitted electrons according
to their kinetic energy, and thereby measure the flux of emitted electrons of a
particular energy).
56
3. A high vacuum environment (to enable the emitted photoelectrons to be analyzed
Figure II. 10: Schematic block diagram of processes involved in the photo emission
spectroscopy
without interference from gas phase collisions).
Figure II. 11: Schematic diagram of the experimental set up used for the X – ray
and Ultraviolet photoemission spectroscopy.
57
3
"
" >
* * HP
B )$
A 8 " 8
&, & 4
58
$
"
B4 L"
, C /
, ?
molecule based materials. Organic vapor phase deposition has also been demonstrated to
materials using the same vacuum evaporation from filaments. For the deposition of high
– temperature metals one may employ e – beam evaporation or sputtering. The later is
particularly useful for large substrates and high throughput production. However,
OLEDs are extremely sensitive to radiation, and special care needs to be taken. In e –
beam deposition, a magnetic field is applied across the substrate to repel electrons and
ions. In sputter deposition, a buffer layer is required to minimize the radiation damage
grown on glass slides pre – coated with transparent ITO with a sheet resistance of 15 -
rinsing in deionized water. They are then cleaned in organic solvents and dried in pure
nitrogen gas. After cleaning, the ITO glass is subject to an oxygen treatment either using
59
UV ozone or oxygen plasma to enhance hole – injection. Single hetero structure devices
are formed by sequential high vacuum vapor deposition of a hole – transport layer such
the Ta boats. The device preparation is completed with encapsulation in a dry argon box.
OLEDs are constructed using glassy and amorphous organic films and thus provide
significant advantages in device fabrication and cost reduction. They are pronouncedly
films.
Thickness
monitor
Shutter Substrate
Source
boats
Vacuum
chamber
Power supply
GND
Figure II. 12: Schematic of the experimental chamber used in our experiments
60
coordinates were recorded using MINOLTA – C 1000 A which has the wavelength range
of 380 – 780 nm, with a wavelength resolution of 0.9.nm/pixel, spectral band width of 5
nm (half band width) and has an accuracy in luminance with ± 2. Current – Voltage
characteristics were recorded on Keithley 2400 source meter coupled with the Keithley
, : E * 7 ; ! 7 $ F
: R $ * <K K ,0 9 D ,",= . 1
& I 7 $ 1 ,.11 ,0 D,
= 4 * ) < -
K KI $ ,0 9 0
$ K K S
61
$ , & /
62
III. 1. Introduction:
Device architecture employing organic molecules to achieve full color display holds
potential to construct cost effective, high brightness light emitting devices (OLED) [1- 4].
Organic / small molecules can play a pivotal role in such architectures, provided,
synthesis and photo physics of such molecules can be tailored. Among many candidates
that are currently being explored, for example: organic – polymer blends [5 - 12], organic
metal chelates in combination with organic dyes have shown interesting display
properties [13 - 17]. Organic dyes on the other hand have strong preference for red and
green light emission [18,19], while stable blue light dyes are scarce and are still being
explored. Alternately organic dyes, which can emit white light, can become crucial for
achieving full color emission [20 - 24]. To design a white light-emitting molecule it is
important to understand the type of charge transfer that is involved. It is well known that
the emission characteristics of the organic molecules are known to change with the
structural packing of the molecules [25 - 29]. Therefore molecular design should be such
that, during the lifetime of the excited species, the electron density could move to the
vicinity of the unexcited segment, in order to fluoresce entirely different, from that of the
molecular species. Such a charge delocalisation can lead to an emission at lower energies
light emission, largely based on its structural conformation. The simplest of such
stereoisomers, where in selective white light emission is observed in one of the stereo
63
isomeric form, namely the cis form of 2,5 – dibenzthiazolyl ethylene. Dynamic photo
luminescent spectral studies give conclusive evidence for the existence of extensive
energy transfers more specifically in cis form of the isomer than the trans isomer. Semi –
empirical calculations show a strong intramolecular energy transfer in the solid form
arising due to an out of plane geometry for the cis isomer. We further demonstrate the
use of cis isomer as an emissive layer in a PFO blended electro luminescent device where
III. 2. Experimental:
Synthesis of stereo specific isomers of DBE in high yields was obtained for the
first time at ambient conditions by a quick synthetic route involving microwave radiation.
thiophenol and maleic/ fumaric acid were taken in a borosil vessel along with
polyphosphoric acid [30] which acts as an acid catalyst as well as a solvent for
microwave thermal heating. After 20 minutes of exposure, the compounds were obtained
by the work – up of the reaction mixture and subsequent washing with dilute NH4OH to
remove excess of polyphosphoric acid. Crude products were recrystallized from methanol
64
and purified using silica column chromatography. Formation and chemical purity of
HS NH 2
COOH
S
N N N
N
S S S
Scheme III.2.: Synthesis of cis – DBE and trans – DBE using microwave
reaction conditions.
15.44
46.39
30.54
10.19
23.14
61.84
10 20 30 40 50 60 70 80 90
16.25
2 θ (deg.)
11.65
*
23.3
*
27.1
32.65
*
41.3
45.05
76.7
85.85
53.4
65
10 20 30 40 50 60 70 80 90
2 θ (deg.)
Figure III. 2.1: shows the powder X – ray diffraction patterns for the cis and
trans conformations. Note the extra reflection, which arises due to the out of
plane geometry of the molecule in comparison to the trans isomer.
65
Figure III. 2.1. shows the powder X – ray diffraction patterns for the
stereoisomers using Cu – K , radiation. Owing to its expected bent crystal structure cis –
isomer is expected to scatter more in the X – ray analysis which is evident from the
diffraction patterns shown. Cis – DBE gives extra reflections compared tot he trans –
DBE, indicative of more distorted structure. Absorption measurements were carried out
were carried out on Hamamatsu C4334. The fluorescence decay was recorded by
stroboscopic sampling using a gating pulse applied to the photo cathode of the GOI,
which could gate the detector for on-times of as little as 90 ps. The fluorescence decay
could then be built-up by varying the delay between the excitation and detection and
1.6 -100
-80
1.4
140 C
o -60
1.2
-40
1.0 Delta H = 437.5 J/gm .
-20
0.8 0
Figure III.2. 2: TG – DSC curves of cis – form of the isomer showing phase
transition from cis - to trans – form of the isomer at 140oC.
AM1/CI empirical models using Hyper Chem. 7.5 molecular modeling software. Figure
66
III. 2. 2 shows the TG, DSC curves of CDBE which shows a phase transition from cis –
form of the isomer to the trans form of the isomer indicated by an endothermic peak at
Absorption spectra of the cis – DBE and the trans – DBE in solid state and in solution
form are shown in Figure III. 3.1. The cis – DBE absorbs below 380 nm and the trans –
DBE absorbs below 270 nm in the solid state. Absorption spectra of the cis –DBE and
trans - DBE in the N, N’ – dimethyl formamide (DMF) at a concentration of 2 x 10-6 M
were recorded. Absorption spectra of the cis – isomer gives absorption edge unusually at
lower energies than that of the trans – isomer wherein conventionally it is expected that
trans form shows absorption at lower energies than cis form of the isomer. This red shift
in the absorption gives clue about the extended delocalisation of electron density in the
cis isomer compared to that of the trans isomer. Absorption spectra in the solid and
solution at low concentrations show similar trend, which is indicative of absence of any
dimeric structure in solid form that can lead to the lower energy absorption in the cis
form.
1.4 0.04
cis - DBE in solid state
trans - DBE in solid state 0.04
Absorbance (solid state)
1.2
cis - DBE in DMF
0.03
Absorbance (2x10 M)
1.0
0.03
0.8
0.02
0.6
0.01
0.4
0.01
-6
0.2 0.01
0.0 0.00
250 300 350 400 450
Wavelength(nm)
Figure III.3.1: Absorption spectra of the cis – DBE and trans – DBE in solid and in solution state.
-6
Solution spectra was recorded in N, N’ – dimethyl
67 formamide at a concentration of 2 x 10 M.
1.0 cis - DBE at 300nm (closed)
cis - DBE at 400nm (open)
0.9
0.7
Intensity
0.6
0.4
0.3
0.1
0.0
400 450 500 550 600 650 700
Wavelength (nm)
Figure III.3.2: Excitation dependant photo luminescent spectra of cis - DBE showing no
change in the emission features with different excitation wavelengths indicating absence
of aggregate formation in the excited state
The possibility of aggregate formation is ruled out based on the observance of emission
spectra with different excitation wavelength. It is well known that when there is
aggregate formation in the excited state the photoemission characteristics will alter with
different excitations. Figure III.3.2 shows photo emissive features at different excitations.
Solid-state photo luminescent (PL) emission characteristics of the cis and the
trans isomers are shown in Figure III. 3. 3.a. When excited at the absorption maximum
(370nm), cis –DBE shows a structured, broad (FWHM ~ 170nm) emission, while the
trans – DBE (absorption maximum 280 nm) shows an unstructured emission (FWHM~
130nm) at higher energy. Figure III.3.3.b, depicts the emissive spectra of CDBE in DMF
–6
solution at a concentration of 2 x 10 M, which shows narrowing of the emission. The
trans form of the DBE doesn’t shows any considerable emission which gives clue about
the existence of intra molecular charge transfer in case of cis – DBE compared to the
trans form of the isomer, which could arise from their differences in the solid state
packing of the isomers [32]. The mechanistic aspects of this interesting behaviour gets
clearer by looking at the nano – second time decay and time resolved photo luminescence
dynamics. The life - time decay traces of the integrated emission between 450 and 600
nm measured in solid state, are shown in the Figure III. 3.4. The PL decay of both the
trans and the cis isomer can be fitted with a double exponential decay model with life
68
times of 0.7 and 3.1ns, and 0.7 and 2.4 ns respectively. However, for the cis – DBE
amplitude of the fast component in the decay is larger compared to that of the trans –
DBE. The differences in decay rates in the cis and the trans isomers give a clue to the
extended energy transfer in case of the former as compared to the trans form of the
isomer as reported by Peng et al. [33]. It is known that with the increase in the
concentration of the species there will be more intra molecular energy transfers which
leads to the faster decay processes.
1.0
cis - DBE
0.8 trans - DBE
Intensity
0.6
0.4
0.2
0.0
450 500 550 600 650 700
Wa v e l e n g t h ( n m)
Figure III. 3.3.a. Photo luminescent emission spectra of cis-DBE (solid line)
and trans - DBE (dashed line) in the solid state with FWHM ~ 170nm and
130nm, respectively.
1.0
0.8
Intensity
0.6
0.4
0.2
0.0
400 450 500 550 600 650 700
W avelength(nm )
Figure III. 3.3.b The emission spectra of cis – DBE in N, N’- dimethyl formamide
at a concentration of 2 x 10 –6 M.
69
10
trans - DBE
1
Intensity
0.1
cis - DBE
0 5 10 15 20
Ti me ( ns )
Figure III. 3.4. Fluorescence decay traces of cis – DBE and trans – DBE in the
solid state.
This phenomenon is observed specifically in the cis form of the isomer owing to
its more closed structure, which resulted in the extended energy transfers in the cis -
isomer, evident from its faster decay compared to that of trans isomer. Nano second time
decay in dilute conditions in DMF solvent in comparison with the decay spectra in the
solid form is shown in Figure III.3.5. The trans form of the isomer doesn’t show any
emission in dilute DMF, but the cis – isomer shows considerable emission, which is
much slower as compared to the solid-state cis – DBE. This can be understood by
considering the fact that intramolecular interactions which become considerably small as
the dilution increases, because of the structural relaxation in the solution [33], contributes
to the slow emission as compared to the decay in the solid state. This also gives clue
about the possibility of non – existence of any intra molecular interactions in case of the
trans – isomer which doesn’t show any emission in the dilute conditions.
70
cis - DBE in dmf
1
Intensity
0.1
0.01
0 5 10 15 20 25 30 35 40 45 50
Time (ns)
10
Dmalsolcis - DBE in solid
1
Intensity
0.1
0 5 10 15 20 25
Time (ns)
Figure III.3.5: Fluorescence decay patterns of cis – DBE in solid state and in N, N’ –
dimethyl formamide
71
nanoseconds. The marked difference between the two isomers can be explained by the
differences in either inter – or intra molecular interactions which could arise out of
structural packing of the two materials. The planar character of the trans – DBE (-C=C-
C-N dihedral angle ~1770) and the out – of - plane twisted structure of the cis – DBE (-
C=C-C-N dihedral angle ~ 400) are likely to introduce differences in the solid – state
packing of these two materials. A planar system like trans – DBE is more likely to
introduce strong interactions coming from co – facial orientations in the solid state. This
could possibly lead to the formation of exciplex or aggregate in the excited state. These
exciplex or aggregate type interactions usually lead to a decrease in the optical band gap;
hence we expected a low band gap in case of trans over the cis isomer. However, the
fact that the out – of - plane cis – DBE shows considerable shift in the spectra towards
red region giving low band gap than the trans form of the isomer suggest that the
differences are probably of an intra – molecular nature.
30
CDBE
25
20
Time (ns)
15
10
0
450 500 550 600 650
Wavelength (nm)
30
25
TDBE
20
Time (ns)
15
10
0 72
450 500 550 600 650
Wavelength (nm)
trans - DBE
1.0
0.8
Intensity
0.6
0.4
2-6 ns
0.2
0.0
cis - DBE
1.0 2 ns
I n t e n s i t y
3 ns
0.8
0.6 4 ns
0.4
5 ns
0.2
6 ns
0.0
450 500 550 600 650 700
Wavelength(nm)
Figure III. 3. 6: Time resolved photo luminescence spectra of cis – DBE and trans –
DBE in the solid state.
73
III. 3.A. Theoretical studies:
The geometries of the molecules in the ground state were optimised with the
semi empirical Austin Model 1 (AM1) method. To calculate the geometries associated
with the lattice relaxation followed by excited state formation, the AM1 Hamiltonian was
coupled to a configuration interaction (CI) technique. Figure III.3.7 shows the frontier
orbitals of both the cis – and the trans – DBE, based on the semi – empirical AM1/CI
calculations [34]. From the frontier orbitals it is evident that the cis – DBE HOMO level
has the charge localized on the benzthiazolate rings while the excited states have an
increased pi – electron density distributed along –N=C-C=C- linkage leading to a reduced
torsion degree of freedom. This results in a decrease in the twist angle between the
vinylene unit and the benzthiazole rings. These orbitals show a redistribution of the
electron density predominantly in the core region of the cis – DBE. However, the
frontier orbitals for the trans isomer gives an entirely different feature wherein even in the
ground state, the HOMO level has a symmetrical electron distribution. The excited state
does not show any significant change in the π – electron distribution, leading to a
predominantly single component emission. This augments our PL spectra as shown in
Figure III.3.3.a. The energy level diagram calculated from AM1/CI model is shown
Figure III.3.8. The optical band gap of the trans form is higher compared to the cis form.
However, the higher LUMO levels of cis isomer namely LUMO +1 and LUMO +2 levels
have discrete energies leading to a featured emission as seen in Figure III.3.3.a. This
argument goes well with our dynamic PL studies (cf. Figure III.3.6.b), which shows a
time dependent red shift in the case of cis - DBE. However in the case of trans isomer
the emission appears to be predominantly from the first excited state to the ground state.
Therefore, we attribute the drastic changes in the emission characteristics of the cis –
DBE to its structural features, compared to the trans – isomer.
74
LUMO + 1 LUMO + 1
LUMO LUMO
HOMO HOMO
HOMO - 1 HOMO - 1
Figure III.3. 7: RHF/AM1-CI electron density distribution of the cis – DBE and
the trans – DBE. The cis – DBE shows strong electron density reorientation in the
excited state which results in strong time dependant red shifted spectra, where as
trans – DBE doesn’t show any redistribution in the electron density.
LUMO+2 LUMO+2
LUMO+1 LUMO+1
LUMO
LUMO
trans-
HOMO
HOMO
Figure III.3.8: The predicted energy level of the cis – DBE and the trans –
DBE. The emission decay in the cis form appears to originate from many of
75
the excited singlet states, leading to a featured broad emission.
III. 4. Electro luminescent Characterization:
Electro luminescent characteristics of the stereo - isomers were studied in detail. Trans –
form of the isomer doesn’t give appreciable light emission when fabricated using
different ways. Being sensitive to the heat treatment we chose solution-processing
methods to deposit the cis – DBE. We fabricated the organic light emitting diode
structure using CDBE as an active layer with polyflourene blend using spin coating
method (see Figure III. 4. 1). Owing to the large HOMO level of PFO ( ~ 5.0 eV), we
employed PEDOT: PSS, as the hole injection layer as well as for the smoothening of the
O O
PEDOT PSS
S n
S O 3-
N N PFO
S S
n
C8H17 C8H17
CDBE
ITO surface. A layer thickness of 100 nm was spin coated on to the substrate using 10%
CDBE as an active layer doped in polyflourene matrix. The device structure is
ITO/PEDOT: PSS/PFO: CDBE/Al. We expected a energy transfer from CDBE to PFO
because of the partial overlap between the absorption band of CDBE and the emission
spectra of PFO which facilitates efficient energy transfer and hence the brightness
efficiency. As expected, this device configuration gave a white light emission with full
width half maxima of about 170 nm at an applied voltage of 8V as shown in Figure III.
4. 2. To rule out the possibility of observed electro luminescence from the oxidized PFO
matrix, we performed all the measurements in strict nitrogen atmosphere under repeated
conditions [35]. Figure III. 4.2.a shows the current – voltage characteristics of the device
structure, which has a threshold voltage of 8V with an initial brightness of 30 cd/m2
reaching 50 cd/m2 at an applied voltage of 14V.
76
1.0
Electroluminescence
0.8
0.6
0.4
0.2
0.0
400 500 600 700
Wavelength(nm)
Figure III .4.2: Electro luminescent (EL) spectra of ITO/PEDOT: PSS/PFO:
CDBE/Al device is shown. cis – DBE is the emissive layer in a PFO host matrix as
shown in the device. Note the close resemblance of the emission curves between the
EL device and the PL spectra of the cis – DBE (cf. Figure 1).
0.06
0.05 Al
Current density (mA/cm )
2
CDBE:PFO
0.04 PEDOT:PSS
ITO
0.03
0.02
0.01
0.00
0 2 4 6 8 10 12 14
Voltage (V)
78
III. 6: Notes and references:
14. D.F. O’.Brien, M. A. Baldo, M.E.Thompson, S. R. Forrest, Appl. Phys. Lett., 75, 4.
1999.
79
15. V. Adamovich, J. Brooks, A. Tamayo, A. M. Alexander, P. I. Djurovich, B. W.
D’Andrade, C. Adachi, S. R. Forrest and M. E. Thompson, New J. Chem.,26, 1171,
2002.
16. J. T. Lim, N.H. Lee, Y.J. Ahn, G.W. Kang, C. H. Lee, Current Appl. Phys., 2,295.
2002.
17. X. Y. Jiang, Z. L. Zhang, B. X. Zhang, W. Q. Zhu, S. H. Xu, Synt. Met. 129, 9. 2002.
18. J. Qiao, Y. Qui, L. Wang, L. Duan, Y. Li, D. Zhang, Appl. Phys. Lett., 81, 4913,
2002.
19. K. O. Cheon and J. Shinar, Appl. Phys. Lett, 81, 1738. 2002.
21. J. T. Lim, N. H. Lee, Y.J. Ahm, G. W. Kang, C. H. Lee, Current Applied Physics, 2,
295, 2002.
22. G. Yu, S. Yin, Y. Liu, Z. Shuai, D. Zhu. J. Am. Chem. Soc., 125, 14816, 2003.
23. P.F. Barbara, L.E. Brus, P.M. Rentzepis, J. Am. Chem. Soc., 102, 5631, 1980.
27. T. Hirsch, H. Port, H.C. Wolf, B. Miehlich, F. Effenberger, J. Phys. Chem. B, 101,
4525, 1997.
80
29. J. A. Hudson, R. M. Hedges, Molecular Luminescence, W.A. Benjamin Inc. New
York, p. 667. 1969.
31. cis – 1,2 – dibenzthiazolyl – ethylene; 1H NMR (DMSO – d6) δ 7.2473 (1H, d, J =
12.4 Hz), 7.9868 (1H, d, J = 7.6Hz), 7.8093 (1H, d, J = 8.04Hz), 7.3504 (1H, t, J =
3.9Hz), 7.456 (1H, t, J = 3.94Hz). IR (KBr; ν/cm-1) 1513, 1435, 937, 758, 647; Elemental
Analysis: %C: 65.23, %H: 3.4; %N: 9.48; %S: 21.20; trans – 1,2 – dibenzthiazolyl –
ethylene; 1H NMR (DMSO – d6) δ 6.9031 (1H, d, J = 16.98 Hz), 7.8312 (1H, d, J=8.28
Hz), 7.7501 (1H, d, J = 8.28 Hz), 7.5017 (1H, t, J = 8 .84 Hz), 7.4377 (1H, t, J = 9.0 Hz),
IR (KBr, ν/cm-1) 1510, 1429, 920, 745, 667.; Elemental Analysis: %C: 65.12, %H: 3.1;
%N: 9.32; %S: 21.80.
32. We resorted to the powder X –ray diffraction data due to unsuccessful attempts to get
single crystals of both the isomers. Powder X – ray diffraction patterns are shown in
Figure III.2.1. Note the extra diffraction peaks for the cis form which indicates a more
distorted structure compared to the trans isomer.
33. K. –Y. Peng, S. -A.Chen, W. –S.Fann, J. Am. Chem. Soc., 123, 11388, 2001.
81
/ @
- $ )$ 4- 5
% %E $ % 5&
F 5
5 0
82
IV. 1. Introduction:
Bis (2 – (2’ – hydroxyl phenyl) benzthiazolate) Zinc (II) complex, ZBZT, has
been studied as an effective white light emissive and electron transport material in
annihilation, for example Pt [3] and Ir [4] complexes. Alq3 is one of the promising
materials for the use in as an electron – transport and emissive material, in combination
with different dye conjugates such as DMQA, and with metal complexes such as PtOEp,
for the full color displays [5]. Single chromophoric white light emission has been a key
issue in ZBZT complex with respect to the electro luminescent emission, which offers
flexibility in the device-making phenomenon [6]. However, the physical properties of this
complex were not well understood; since the photo and electro luminescent properties of
this material were explained based on the presumed monomeric structure [7]. More
recently, Yu et al have reported the crystal structure of this compound, demonstrating the
unique dimeric nature of this complex, as shown in Figure IV.1, wherein it exits as
[ZBZT] 2 in both powder and in the amorphous thin film form, [8]. Using the
photoemission, emission decay and the electrochemical methods, we show that within the
dimeric form of the complex, the electron density distribution was localized on the non-
bridged benzthiazolate moiety in the excited state and hence the emission and the
related to the broadband emission were understood based on the exciplex formation at the
organic – organic interface. We further substantiate the experimental results with semi-
83
distribution in LUMO levels of the complex to be more localized on the non - bridged
N
N
O O
Zn Zn
O O
N
N
84
IV. 2. Experimental:
IV. 2.A: 2 - (2’ - hydroxyl phenyl) benzthiazole, (BZT): BZT was synthesized for the
first time employing microwave radiation as shown in scheme IV.1. Figure IV.2 shows
OH
NH2 COOH HO
N
+
SH
S
IV. 2.B: bis (2 - (2 - hydroxyl phenyl) benzthiazolate) Zinc(II): Zinc complex of 2,2 –
Acetate and BZT in ethanol and stirred for half an hour at 60oC. A pH of 8 – 9 was
maintained for complexation. Zinc complex was vacuum sublimed prior to use. m.p.
450oC. 1
H – NMR, 7.2483, 7.432(q, J = 6.84Hz), 6.9312 (td, J = 7.8 Hz, 8.56 Hz),
7.4112(d, J = 3.78 Hz), 7.6567 (d, J = 7.84 Hz), 7.8569 (d, J = 8.04 Hz), 8.2993 (d, J =
6.67Hz). IR, cm-1 (KBr): 3058.06, 1709.6, 1541.8, 1343.43, 975.23, and 750.7. Figure
IV.3 shows the DSC curve of ZBZT. As can be seen a large endothermic transition is
86
45
DSC- ZBZT
40
35
25
20
15
10
Scanning Calorimeter. The cyclic voltamograms (CV) of the ligand and complex were
reference electrode and platinum wire as an auxiliary electrode supported in 0.1M (n-Bu)
measurements were made using a high- repetition rate pico second laser coupled to a time
photo multiplier (Hamamatsu 2809). The samples were excited at 375 nm laser pulses
and the emission at their PL peak maxima were collected. The full-width at half-
87
maximum of the instrument response function was approximately 200 ps. Typical count
rate for fluorescence decay measurements was about 4000-5000/s (~ 0.5% of the
excitation rate) and the typical peak count was 5-10 x 103[9]. All the semi – empirical
calculations were carried out using Hyperchem molecular - modeling lab software.
coordination with the benzthiazolate ligands and have distorted trigonal bipyramidal
geometry. Energy minimized structure of the dimeric Zinc complex is shown in Figure
IV.1. Two out of four benzthiazolate ligands are involved in a bridged conformation
between two Zinc atoms while the other two-benzthiazole ligands are solely attached to
either of the Zn atoms. From the single crystal X – ray data, calculated Zn – O bond
lengths for the non – bridging ligands are 1.962 Å, where as those in the two bridging
ligands lengthen to 2.058 Å. Similar observations are predicted for Zn – N bond lengths.
DSC curve (Figure IV.3) shows a single endothermic transition at 3100C, which confirms
the existence of a dimeric species in accordance with the literature value [8]. Photo
luminescent behavior of the ligand and complex studied in solid state are shown in Figure
IV.4a. BZT and [ZBZT] 2 were excited at 325 nm owing to their broadband absorption
spectra. Figure IV. 4b shows the optical image of the vacuum-evaporated film of [ZBZT]
2 on a glass substrate. Film evaporation was done at a base pressure of ~10–6 mbar at a
rate of 0.2 – 0.3 nm / sec. Optical micrograph shows smooth and uniform [ZBZT] 2 films.
Figure IV .4 shows the photo luminescent spectra of the ligand, BZT, and of the
complex in solid state, when excited at 325 nm. In the case of BZT molecule, an
unsymmetrical structured emission with peak maxima at 511 nm having a shoulder at 550
88
nm was observed. BZT has been studied extensively in the solution state, owing to its
interesting proton transfer kinetics. Barbara et al demonstrated that the two intense
emission peaks at 480 nm and 520 nm could be attributed to the H – transferred keto –
enol tautomeric structures respectively in the solution state [10,11]. However, in the
solid state, energetically favored “enol” form is preferred. As a result, in the solid state,
the peak at 480 nm completely disappears due to the fact that the torsional motion is
virtually frozen so that the H – bonded enol conformer is preferred energetically. The
in the molecule. However, when complexed with the Zinc metal ion, we observe a blue
shift (λmax = 485 nm), in contrary to the usual red shift observed for the complexes. This
0.6
0.4
0.2
0.0
400 500 600 700
Wavelength(nm)
Figure IV. 4: (a) Photo luminescent spectra of ligand and the complex in
solid state. (b) shows the 80 nm film forming ability of vacuum evaporated
[ZBZT] 2 at a rate 0.2 – 0.3 nm/s at 10-6 mbar pressure.
89
1000
Intensity BZT
fluor. lifetime = 4.822 ns.
100 [ZBZT]2
fluor. lifetime(τ1) = 2.354ns;
fluor. lifetime(τ2) = 5.236 ns;
Average Lifetimes: 3.027ns
10
Figure IV. 5: Photo luminescent time decay spectra of BZT and [ZBZT]2 excited
at 315 nm. BZT follows a single exponential decay pattern while [ZBZT]2 follows
a double exponential decay profile with average lifetimes of 4.82 ns and 3.02 ns
respectively. Also shown the residual fits of ligand and complex, which gives a
good minimum χ2 value.
The fluorescence decay curves of the ligand and complex in solid state on
excitation at 325nm are shown in figure IV. 5. The analysis of the decay curves was
performed by non - linear least squares routines minimizing the χ2 parameters (~ 1) using
the supplied software. BZT fits to a single exponential decay pattern with a lifetime of
4.8 ns, where as ZBZT fits to a double exponential decay model with life times of 2.3 ns
90
(τ1) and 5.2 ns (τ2) respectively. The second lifetime component of the complex has a
close match with that of ligand that reveals the dominance of the benzthiazole moiety in
sweeping ZBZT in cathodic direction one oxidation peak at –1.82 V which matches
which gives clue about the ligand controlled transport in the complex which was in good
agreement with the observations of the time decay PL measurements that the
0.002
0.000
-0.002
-0.004
-0.006
-1.4 -1.6 -1.8 -2.0
Vol t a ge ( V)
91
IV. 4: Semi empirical calculations:
PM3 – CI calculations [12] shows (see Figure IV. 7) that the electron density
distribution in the filled π -orbitals (HOMO’s) and the unfilled orbitals (LUMO’s) were
mainly dominated by orbitals originating from those of the 2- (2- hydroxyphenyl)
benzthiazolate ligand in the complex.
LUMO
MO
HOMO
92
Structural Parameter Calculated* Reported**
Zn (1) – O (1) 1.9708 1.962
Zn (1) – O (2A) 1.9977 2.017
Zn (1) – O (2) 2.201 2.058
Zn (1) – N (1) 1.9955 2.095
Zn (1) – N (2) 2.0487 2.170
O (1) – Zn (1) – O (2A) 99.1 97.4
O (1) – Zn (1) – O (2) 164.21 172.18
O (2A) – Zn (1) – O (2) 62.49 76.13
O (1) – Zn (1) – N (1) 90.72 87.37
O (2A) – Zn (1) – N (1) 106.76 120.09
O (2) – Zn (1) – N (1) 87.01 99.63
O (1) – Zn (1) – N (2) 96.24 97.26
O (2A) – Zn (1) – N (2) 120.05 117.12
O (2) – Zn (1) – N (2) 79.21 82.13
N (1) – Zn (1) – N (2) 118.61 121.38
Zn (1A) – O (2) – Zn (1) 100.61 103.87
Tabel IV. I: showing PM3 calculated (this work) in comparison to the reported
literature from Yu et al.
The contribution from the Zn2+ ions was distinctly small. We observe the HOMO’s of
[ZBZT] 2, which were localized on the phenoxide ring of the two non-bridging ligands,
whereas the LUMO’s electron density distributes on the phenoxide and thiazolyl rings of
the two bridging ligands. Therefore, the electronic π-π* transitions in [ZBZT] 2 molecule
were localized on the benzthiazolate rings, from the non-bridging ligands which
contributes to the blue shift in the emission spectrum. Theoretical UV/VIS spectral
Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) that
exactly matches with that of the experimental value (absorption edge below 380nm), with
93
an oscillator strength length of 0.1782. The above conclusions were in agreement with
quantum efficiency φs ~ 0.54 [13]. The quantum yield was calculated according to the
reported literature [14]. All solutions were taken at 2x10-6 M dilutions. The quantum
yield obtained for [ZBZT] 2 is 0.242, which shows that [ZBZT] 2 has very high photo
luminescence efficiency.
nm) /Al (1000 nm). TPD was used as a hole transport material in the EL device, [ZBZT] 2
was used as the electron – transport and emissive layer. ITO – coated glass with a sheet
resistance of 50 Ω/ was used as the transparent anode. All the organic layers were
-6
deposited successively onto the ITO glass at 5 x 10 Torr. The deposition rates for the
organic layers and the metallic layers were 0.2- 0.3 nm/Sec. The emissive area was 4 mm
x 4 mm. Figure IV.8a shows the EL spectrum of [ZBZT]2 at various current densities.
Figure IV. 8b shows the current – voltage – luminance spectra of the device which shows
typical diode characteristics. The EL emission spectrum shows a broad emission with a
full width half maximum of more than 220 nm with CIE coordinates of 0.33 and 0.29,
which is a close match to a clear white emission. The color coordinates of the
electroluminescent spectra remained constant with the applied voltage, which is good for
the use as electroluminescent devices as shown in figure IV. 9. The broadening of the
spectra compared to the photoluminescence spectra gives clue about the emission from
94
the interface between TPD and [ZBZT]2. The probable mechanism could be the
formation of exciplex of TPD – [ZBZT]2 at the interface of the TPD and [ZBZT]2 which
leads to the broadening of the emission spectra. The exciplex is a result of charge transfer
interaction between the excited/ground state of the donor and ground/excited state of the
acceptor [15]. Under the electrical excitation, the exciplex should be formed by the
confinement of the carriers injected from the opposite electrodes between donor and
acceptor molecules. Figure IV.10, shows the exciplex emission process of ITO/ TPD:
[ZBZT]2 /Al device under electrical bias. The lower IP value of TPD (-5.4 e V) than
[ZBZT]2 makes holes injected readily into and transported via the HOMO of TPD. The
higher electron affinity of [ZBZT]2 provides the preferable electron transport pathway
through the LUMO of [ ZBZT]2. When injected, holes and electrons encounter each
other, they can form a hole – electron pair, i.e., TPD+ - [ZBZT]-2 exciplex, and they
recombine radiatively. To further prove our point we fabricated EL devices with three
different thickness of active layer, [ZBZT]2, since the formation of exciplex is sensitive
to the thickness of the active layer [16]. Figure IV. 11 shows the EL spectra of different
thickness of [ZBZT]2 active layer. As can be seen recombination zone and hence the
0.2 mA
0.8 0.5 mA
1.0 mA
Electroluminescence
1.6 mA
0.6
0.4
0.2
0.0
400 500 600 700
Wavelength (nm)
95
2 3
Luminance (Cd/m2)
Current (mA)
1 2
0 1
-1 0
30 35 40 45 50 55
Voltage (Volts)
Figure IV. 8: (a) Electro luminescent emission spectra of ITO/TPD/ [ZBZT]2/Al at
various current densities. (b) shows the dependence of current density and luminance to
the voltage.
1.0
X - Co-ordinate
Y - Co-ordinate 0.8
Co - ordinates
0.6
0.4
0.2
0.0
55 50 45 40 35 30
Voltag
e
electro luminescence peak maximal shifted with either decreasing or increasing thickness
of the active layer gives the clue about the formation of exciplexes at the interface of
ZBZT – TPD. The device with ZBZT layer thickness of 60nm, 70 nm and 95 nm shows
97
60 nm
1.0 70 nm
95 nm
80 nm
0.8
Electroluminescence
0.6
0.4
0.2
0.0
400 500 600 700
Wa v e l e n g t h ( n m )
Figure IV. 11: Electro luminescence spectra of ITO/ TPD/[ZBZT] 2 /Al, with 60
nm, 70 nm, 80nm, 95 nm active layer thickness
Multiple Gaussian fits on the observed electroluminescent spectra yields a fair conclusion
that there might be five different species involved in the electroluminescent spectra with
a broad peak emission at lower energies, which is a result of exciplex formation. Figure
IV. 12 show the Gaussian fits to the electroluminescent spectra along with the analysis
table.
98
ITO/TPD/ZBZT/Al
1.0
0.8
Electroluminescence
0.6
0.4
0.2
0.0
400 500 600 700
Wa v e l e n g t h ( n m)
Figure IV. 12: Peak Area fitting of ZBZT – Electroluminescence, which fits to
multiple Gaussian fit showing a broad emission feature at lower wavelength as a
result of exciplex formation between the interface of ZBZT and TPD.
Further we show that the introduction of a insulating layer in the form of thin LiF which
has a large band gap of 12eV, which is know to facilitate the electron injection to a
greater extent should appreciably shift the peak maxima and also the broadening of the
properties of electroluminescent spectra, as can be seen spectra maxima got shifted to 475
nm in comparison with the electroluminescent spectra with out LiF insertion which peaks
at 583 nm.
I0.05mA 475
1.0 I0.11mA
ITO/TPD/Zn(BZT)2/LiF/Al
I0.15mA
0.8
EL Intensity
0.6
0.4
0.2
0.0
1E-6
1E-7
1E-8
1E-9
1E-10
1E-11
1E-12
0 10 20 30 40 50
Voltage (Volts)
Figure IV. 13: (a) shows the effect of LiF insertion in the device structure (b) shows
I- V characteristics of the LiF inserted device.
100
The full width half maxima of the spectra get reduced from ~ 200 nm to 90 nm indicative
of exciplex formation at the interface. However this device structure is not very reliable
as our experimental limitations in depositing thin film of LiF yield poor film quality.
As for our best devices with simple device structures we obtained a maximum
luminance of 200 cd/m2 (corrected) an applied voltage of 24 Volts as shown in the Figure
IV. 14. Inset to Figure IV.14 shows the picture of pixel appearance of 5 x 5 mm at an
applied voltage of 24V. Figure IV. 15 shows the current – Voltage – Luminance
1.0 16 Volts
20 Volts
24 Volts
25 Volts
0.8
EL Intensity
0.6
0.4
0.2
0.0
400 500 600 700
Wavelength (nm)
101
-3
1.4x10
40
-3
1.2x10
35
Luminance (Cd/m2)
-3
1.0x10
Current (Amp)
30
-4
8.0x10 25
-4 20
6.0x10
15
-4
4.0x10
10
-4
2.0x10
5
0.0 0
14 16 18 20 22 24 26
Voltage (Volts)
property of the complex, [ZBZT]2 which otherwise is not clear when considering
102
References:
1. Y. Hamada, T. Sano, H. Fujii, Y. Nishio, H. Takahashi and K. Shibata, Jpn. J.
4304,2001.
4076,1999.
550,2003.
2 ,295,2002.
8. G. Yu, S. Yin, Y. Liu, Z. Shuai and D. Zhu, J. Am. Chem. Soc., 125, 14816,
2003.
103
11. P. F. Barbara, L. E. Brus, and P. M. Rentzepis, J. Am. Chem. Soc, 102, 563,1980.
and quantum mechanical calculations (PM3, RHF, closed shell, default settings).
Excited energy state analysis and analysis of electronic absorption spectra were
carried out using ZINDO/S-SCF-CI calculations using Argus Lab 3.01 molecular
Modelling software.
17. Z. R.Hong, O. Lengyel, C.S.Lee and S.T.Lee, Organic Electronics, 4, 149, 2003.
104
8*) 7 4
K
A '& "
'&5" ( ( ! ' (A '! G *
+ (
This chapter deals with a study on the synthesis and optical properties of benzthiazole
complexes of group 13 elements namely Aluminum, Gallium and Indium metal ions
together with Zinc benzthiazole complex as they form a family of complexes showing
systematic and interesting luminescent properties. These are grouped as HALF CROSS
have studied in detail the Gallium based complexes. The Gallium based device has been
105
V. I. Introduction:
Group 13 elements in the periodic table has always been fascinating to both
chemists and physicists due to their interesting properties related to the inorganic
semiconductors like InAsP [1] , GaN [2], InP [3], InGaAs [4] etc., and a variety of
organo metallic complexes [5-10], more specifically Alq3, Gaq3, Inq3 [11,12] complexes.
A rich chemistry and physics involved in these metal ion complexes enthusiasts’
candidates for the use in light emitting diodes show promise because of their distinct
complexes of group 13 metal ions. We have studied Aluminum, Gallium, Indium and Zinc
(HCC). All these metals occupy distinct positions in the group 12 and 13 of the periodic
table.
the solid state. The other objective is to spectroscopically understand the interfacial
effects of the metal – organic (M –O) and organic – organic (O – O) interfaces in the
electro luminescence devices, with specific reference to Gallium (III) complex. Another
106
objective is to improve on the device performance employing benzthiazole molecules
based on their charge mobility values. To this end we show 2,5 – dibenzthiazolyl
V. II .A. Synthesis:
benzthiazole (BZT) (synthesis of BZT was described in chapter II) and Aluminum iso –
propoxide in ethanol under nitrogen atmosphere. Total reaction time was 5 hours.
Melting point: > 2000C; Appearance: Yellowish white solid. Solubility: Hot N, N’ –
V. II. 2: Tris (2 – (2’ – hydroxy phenyl) benzthiazolato) Indium (III) complex (IBZT):
benzthiazole (BZT) (synthesis of BZT was described in chapter II) and Indium Chloride
in ethanol under nitrogen atmosphere. Total reaction time was 3 hours. Melting point: >
Ethanol, reflux
In Cl3 + C13H9NSO 3 hours, N2 atms.
In -( C13H8NSO)3 --------------- (2)
107
V. II.3: Tris (2-(2’ – hydroxy phenyl) benzthiazolate) Gallium (III). dihydrate complex
benzthiazole (BZT) (synthesis of BZT was described in chapter II) and Gallium Chloride
in ethanol under nitrogen atmosphere. (As handling GaCl3 is difficult, all transfers and
weighing were done in glove bag under nitrogen atmosphere). Total reaction time was 5
hours. Melting point: 2400C; Appearance: Bright green solid. Solubility: Hot N, N’ –
GBZT was done in the inert atmosphere. Figure V.II. shows the TG analysis of GBZT
complex. The first weight loss of the TG corresponds to two water molecules, which were
that the weight loss in the TG goes to zero unlike other metal complexes. This could be
due to the low melting point (!) of Gallium metal 29oC, which sublimes at even ambient
temperatures.
2.5 -30
-25
2.0
Heat Flow Endo Up (mW)
-20
-15
1.5
Weight (mg)
-10
1.0
-5
0
0.5
5
0.0 10
50 100 150 200 250 300 350 400 450 500 550 600
o
Temperature ( C)
Figure V.II.1: Thermo gravimetric and differential thermal analysis curves
of GBZT under N2 atmosphere. 108
Table V. 1: showing the thermo gravimetric analysis of GBZT complex
V.II.4: bis (2-(2’ – hydroxy phenyl) benzthiazolate) Zinc (II) complex (ZBZT):
Although complete description of synthesis and properties of this complex has been
extensively discussed in Chapter IV, we show the synthetic conditions of Zinc complex for
Powder X – ray diffraction patterns of the Aluminum, Gallium, Indium and Zinc
benzthiazole complexes are shown in Figure V. II.2. All the complexes indicate a weakly
crystalline pattern with more reflections in the lower angles indicating on an average a
larger unit cell, >5 Å. The patterns are indicative of a more distorted structure. Although
there are some similarities in the X – ray patterns (for example, see the patterns of
Indium and Zinc complexes), none of the complexes appear to be clearly isomorphous
one with the other, restricting our efforts to prepare solid solutions of these complexes.
109
Intensity (a.u.)
isomorphism
ZBZT
20.5
IBZT
20
ABZT
20.85
GBZT
22.55 22.55 22.7
24.8 25.25
26
26.9
27.85
30
31.35 31.5
32.75
35.1 34.4
39.3 39.6
40
41.1 41.55
44.7 44.85 45.6
46.8 46.35
110
48.55 48.3
50
51.6 50.85
53.55
2 θ (degree)
56.8 57.25 56.6 57.75
60
61.35
63.05 63.2 63.8
65.35
67.15
68.15 68.6
70.75
70
71.8
73.1
74.8
77.25 77.1
80
Figure V.II.3. shows the photo luminescent spectra of the half cross complexes in
the solid state. It is noteworthy to observe a systematic shift in the emission maxima with
the size of the metal ion. The observations are tabulated in Table V. 2
IBZT
1.0
GBZT
ZBZT
ABZT
0.8
0.6
Intensity
0.4
0.2
0.0
400 450 500 550 600 650 700
Wavelength (nm)
1.0
0.8
0.6
Intensity
0.4
IBZT
0.2 GBZT
ZBZT
ABZT
0.0
450 465 480 495 510 525
Wavelength (nm)
111
Table V. 2: Photoluminescent emission parameters of the half cross complexes
single photon counting method-using Nd: YAG laser under ambient conditions. Figure V.
II.4 shows the photo luminescent decay patterns of ABZT, GBZT, and ZBZT at room
temperature and recorded at 77K. Photoluminescent decay analysis of the ABZT at room
temperature fits to a double exponential decay model (refer to equation V. II.1) with life
times of τ1 = 0.13 ns and τ2 = 0.49 ns with an average lifetime of 0.301 ns. The first
lifetime component of the complex was faster in decay, which was due to the possible
ligand to metal charge transfer. Low temperature decay (77K) fits to a double
exponential decay with lifetimes of 4.07 ns and 9.02ns respectively. The decay
measurement at 77K shows much slower decay with an average lifetime of 5.136 ns.
112
at 300K
1000
GBZT
Intensity 100
ZBZT ABZT
10
0 5 10 15 20 25 30 35
Time (ns)
at 77K
1000
ABZT
Intensity
100
ZBZT
GBZT
10
0 5 10 15 20 25 30
Time (ns)
Figure V.II.4: shows the PL decay patterns of the half cross complexes at room
temperature and at liquid nitrogen temperature.
exponential decay with lifetimes τ1 = 1.41 ns and τ2 = 5.38 ns with an average lifetime of
3.35 ns. Decay profile at 77K shows decay which fits to double exponential with life times
τ1 = 3.74ns and τ2 = 7.549 ns with an average lifetime of 3.78 ns. It is interesting to note
that in the case of GBZT, the average life times are independent of temperatures showing
113
that the spin – orbit coupling contribution from the metal ion is less, which differs from
the photo physical behavior of the Aluminum complex, although they belong to the same
group in the periodic table. ZBZT PL decay measured at room temperature fits to a
double exponential decay with lifetimes of τ1 = 2.35 ns and τ2 = 5.23 ns with an average
lifetime of 3.02 ns. Decay profile at 77K shows decay which fits to double exponential
with life times τ1 = 2.90 ns and τ2 = 4.66 ns with an average lifetime of 3.34 ns. It is
interesting to note that in case of ZBZT complex the average life times are independent of
temperatures similar to Gallium complex. Table V.3 tabulates all the observations on the
Table V.3: shows the PL decay analysis of the half cross complexes. Note the
similarities in the lifetime trend variation of ZBZT and GBZT
300K 77K
GBZT
1.41 5.38 3.35 3.74 7.54 3.78
ZBZT
- - - - - -
IBZT
114
V. III: Electroluminescent properties of tris (2-(2 – hydroxy phenyl) benzthiazolate)
Gallium (III) complex:
Similar to ZBZT complex (as discussed in the preceding chapter), which was
employed as an emissive layer in the EL device, we have made a device employing GBZT
complex in the device structure such as ITO/TPD (50nm) /GBZT (80 nm)/Al (100 nm). As
in the case of ZBZT, ITO acts as the anode, TPD as a hole transport layer and GBZT as
an electron transport and emissive layer. Aluminum was used as a cathode. From the TG
data we have optimized the evaporation conditions for the GBZT complex. However
during the device fabrication, we observed that GBZT needed slower evaporation for the
deposition at the rate of 1-2 Å/sec, probably due to its poor thermal conductivity. The
pixel size was 3 x 3 mm2. All usual procedures were adopted, like patterning and
ozonization of ITO surface before depositions. ITO used here has a sheet resistance of 50
Ω/ .
emission around 620 nm with a FWHM of around 170 nm, a feature completely different
from the photo luminescent emission (PL emission maxima was around 483 nm with a
FWHM ~ 80nm). We observe a distinct change in the electro luminescent emission curve
compared to the photo luminescent emission is shown in Figure V.III.1 This difference
between the PL and EL spectrum suggest that the recombination zone is completely
dominated by the interfacial properties of GBZT and TPD in the device structure. Such a
contrast between photo luminescent and electro luminescent spectra is noted for the Ir
115
EL
1.0 PL
0.8
Intensity 0.6
0.4
Al
GBZT
TPD
0.2 ITO
0.0
400 500 600 700 800
Wavelength (nm)
Figure V.III.1: Electro luminescent spectra of ITO/TPD/GBZT/Al, where in TPD was
used as a hole transport and GBZT was used as an electron transport and emissive layer.
interpreted based on the interfacial energy levels alignment. In the subsequent sections,
we show the Organic - Organic (O – O) interfaces deposited on the Gold substrate and
the ITO substrate using X – ray photoelectron and Ultraviolet Photo electron
spectroscopy to investigate the mechanism for the observed red shift in the EL spectra
Before proceeding to the actual interfacial alignments used in the device structures,
we would study the O –O interfacial properties on poly crystalline gold (Aupoly) substrate.
116
1. To determine the HOMO level of GBZT and TPD on the Au substrate.
Based on the UPS valence band spectra and the onset spectra we have constructed the
energy level diagram for the interfaces of Au/GBZT/TPD. (The detailed experimental
V.1) The HOMO level of GBZT deposited on Au was at 0.81 eV with respect to Au
Fermi level, showing a value of 5.31 eV. The LUMO energy level was calculated
from the difference in optical band gap and the HOMO level was 2.11 eV, (EHOMO –
between the vacuum level and the HOMO onset of GBZT. The value of ionization
potential of GBZT is 4.81 eV. Figure V.IV.1 shows the energy level diagram of the
Au/GBZT/TPD.
EV
0.5eV
0.6 eV
2.11eV LUMO
2.9 eV
4.5 eV
EF
0.81eV 1.8 eV HOMO
Au/GBZT/TPD
where as the vacuum level shift of 0.1 eV is observed between GBZT /TPD interface.
Such a large shift in the vacuum level observed for the metal – Organic (M – O)
interfaces due to the formation of large interface dipoles in the literature. [14]
From the above energy level diagram (Figure V. IV.1) it is evident that the HOMO
of TPD agrees well with the reported literature [15]. Further this give a clue that the
O – O interface between TPD and GBZT doesn’t seem to alter the HOMO levels,
shifts in the vacuum levels of both GBZT and TPD with reference to Au substrate
order to see if any chemical effects which could arise in the O – O interface we look
at the core level spectra of C – 1s. Figure V.IV.2 shows C – 1s spectra of XPS with
the sequential deposition of GBZT, TPD and Au. The C – 1s peak undergoes a 0.5
eV shift to higher BE with the first few angstrom (100Å) of GBZT deposition on Au
surface and its position and shape remain basically unchanged thereafter. The shift in
the C –1s spectrum is indicative of the formation of interface dipole between Au and
GBZT. All the spectra were similar in shape with no substantial change in the peak
Similar shift of 0.23 eV was also observed between the TPD and Au interface
towards the lower energy region. Thus based on the above observations, we rule out
the possibility of any distinct chemical interactions occurring between the layers,
which could result in a red shift in the EL when compared to the PL.
118
T P D - Au C - 1s
0 .2 3 e V
G B Z T -T P D
0 .4 9 e V
G B Z T -P artial T P D
0 .4 5 e V
Au - w ith fu ll G B Z T co verag e
0 .5 e V
Au - p a rtial G B Z T layer
Figure V.IV.2: shows the XPS spectrum of C –1s. Note the absence of peak shift
and peak shape between organic – organic interfaces, which is indicative of absence
of interface dipole and chemical interaction between the GBZT-TPD interfaces
respectively.
The other possible reason could be the interfacial energy alignments in the actual
device structure rather than the interfacial interactions. We have further investigated the
interfacial effects by studying the actual device structure, which we have used for the
Figure V.IV.3 shows the valence band spectra of ITO/TPD/GBZT. From the
valence band spectra it can be seen that evolution of respective HOMO levels at the
interfaces for TPD and GBZT from which we calculated the HOMO and from the optical
band gap the LUMO levels. TPD valence band spectra show a HOMO of 1.81 eV relative
119
to the ITO. With the deposition of GBZT, a peak at 0.81 eV, corresponding to the HOMO
level of GBZT is observed. It is note worthy that the HOMO levels remains practically
ITO/TPD/GBZT
ITO/TPD
0 2 4 6 8
Binding Energy (eV)
V.IV.4. The vacuum level shift in the ITO/TPD/GBZT doesn’t follow the usual “ladder”
needed for the smooth electron/hole transport. For example the vacuum level shift in the
120
ITO/TPD interface is positive (0.82 eV) while the vacuum level shift in the
GBZT
0.19 eV
TPD
0.82 eV
ITO
9 8 7 6 5 4 3 2 1
Binding Energy (eV)
Figure V. IV.4: shows the onset spectra of ITO/TPD/GBZT showing a vacuum level
shift of 0.82 eV between ITO/TPD interface where as it shows a shift of –0.19 eV
between TPD/GBZT.
Based on our results on the valence band and onset spectra we show the energy level
diagram in the device structure ITO/TPD/GBZT (as seen in Figure V.IV.5.) It is known
in the literature that dipoles occur at hetero layer interfaces between materials of different
interfaces [15]. In such cases, a partial charge is expected to get transferred from the low
ionisation energy constituent to the high electron affinity molecule. Such donor/ acceptor
121
emission at lower energies. This argument goes well with our experimental data on
electro luminescence. Recall that the photo luminescent and electro luminescent spectra
of the GBZT differ drastically, “where a broad totally red shifted EL” is observed
compared to the photo luminescent spectra. From the energy level diagram it is evident
that there could be a partial energy transfer from low ionisation potential of TPD to the
leading to the emission at lower energies causing a red shift in the electroluminescent
spectra. This cumulative effect could be attributed to the ITO/TPD and TPD/GBZT
interface.
0.19 eV
0.82 eV
1.81 eV
2.61 eV
4.2 eV
ITO 0.81 eV
1.81 eV
TPD GBZT
Figure V.IV.5: shows the energy level diagram of the device ITO/TPD/GBZT
122
Figure V.IV.6 shows the C – 1s spectra of the TPD/GBZT interfaces in ITO/TPD/GBZT
device structure. The C – 1s spectra shows a marginal shift of 0.09 eV towards low
binding energy that gives clue about the formation of interfacial dipole between O – O
interface ie., TPD/GBZT. Note that the shape of the C – 1s spectra for all depositions
shows no shift in the peak, but the shape of the spectra changed considerably forming a
low binding energy shoulder. The change in the spectral shape gives clue about the
formation of different chemical environment around the nitrogen atom probably due to
0.09 eV
TPD
TPD
Figure V.V.1 shows the current – voltage characteristics of the device structure
showing a threshold voltage of 35 V, which follows the behavior of the typical diode. (A
diode current density will linearly increase with the light out put as seen in Figure
V.V.1). This device shows an initial brightness of 20 cd/m2 and reaches to 200 cd/m2 at
applied voltage of 40 V.
12
0.7
0.6
Luminance (arb.unit)
10
0.5
Current (mA)
0.4
8
0.3
0.2 6
0.1
0.0 4
20 30 40 50
Voltage (V)
Figure V.V.1: Current – Voltage – Luminance characteristics of the EL device structure
with the configuration ITO/TPD/GBZT/Al, following typical diode characteristics.
desired values. In our efforts to further improve on the performance of this device, we
show the use a high electron mobility benzthiazole molecule namely 2,5 – dibenzthiazolyl
124
V.VI: Influence of 2,5 – dibenzthiazolyl thiophene as an electron transport layer on the
GBZT device structures:
be seen in the Figure V.VI.1 the threshold voltage of the device gets considerably
reduced with the TBZT deposition from 35 V to 15 V. This also highlights the electron
transport ability of TBZT in the device structure. The detials of electron mobility
measurements are documented in Appendix V.2. Figure V.VI.2. shows the cumulative
of the remarkable feature observed apart from the lowering of the threshold voltage is the
movement of the recombination zone towards the anodic direction resulting in a blue
shift of the order of 25 nm, which demonstrates the uniqueness of TBZT as an electron
injection layer.
0.006
-
Al
0.004
TBZT
GBZT
Current (mA)
TPD
ITO
0.002 +
0.000
13 14 15 16
Voltage (v)
125
1.0
GBZT
GBZT/TBZT
0.8
Intensity
0.6
0.4
0.2
0.0
400 450 500 550 600 650 700 750
Wavelength (nm)
Figure V.VI.2: shows the effect of TBZT on the GBZT electroluminescent properties with
device structure ITO/TPD/GBZT/TBZT/Al. An improvement of threshold voltage of the
order of 20 V was obtained by introducing a thin layer of TBZT (10nm) into the device
structure ITO/TPD/GBZT/Al.
Having observed a distinct change in the threshold voltage with the incorporation
Appendix-2; we will show here the important observations from the XPS and the UPS
studies on ITO/TPD/GBZT/TBZT.
From the valence band spectra it can be clearly seen that evolution of respective HOMO
levels at the interfaces for TPD, GBZT and TBZT from which we calculated the HOMO
levels. The LUMO levels of the respective molecules were calculated by taking
differences between the optical band gap and the HOMO level. TPD shows the HOMO
126
level at 1.81 eV relative to the ITO. With the deposition of GBZT, a peak at 0.81 eV,
corresponding to the HOMO level of GBZT was observed. Similarly with the deposition
TBZT UPS
Partial TBZT
GBZT
TPD
0 2 4 6 8
Binding Energy (eV)
127
Energy level diagram is constructed based on the UPS valence band spectra of
ITO/TPD/GBZT/TBZT/Au and the ONSET spectrum for the same device. Charge
exchange, chemical bonds and chemistry – induced effects are usually expected at
metal – organic interfaces and are not expected to occur at O - O interfaces. However,
as can be seen from the energy level diagram as shown in Figure V.VII.2, we
observed large dipoles at the O - O interfaces in our device structure. The energy
barrier for charge injection between the TBZT and GBZT is only 0.2 eV facilitating
the enhanced electron injection, which is contributing to the lowering of the threshold
0.19 eV
0.82 eV 0.25 eV
1.81 eV
2.61 eV 2.1 eV
4.2 eV
700
Figure V.VII.2: showing the energy level band diagram of the layer deposited
ITO/TPD/GBZT/TBZT/Au
The N - 1s spectra at the TPD/ GBZT interface is virtually unchanged. However with the
nitrogen atom. A similar shift towards a lower binding energy is observed in S – 2p core
level spectra due to a dominant electron density around the ‘S’ atom. This is evident with
TBZT N-1s
1.42 eV
Partial TBZT
0.59 eV
GBZT
TPD
seen with the partial coverage of TBZT on GBZT a shift of 1.11 eV is observed in the
XPS spectra of S – 2p. Such a large shift in the spectra in the S – 2p spectra is unusual. It
is interesting to note that with the complete coverage of TBZT on GBZT the shift in S-
2p get reduced to 0.62 eV ( a shift of 0.49 eV from the partially covered TBZT). Such a
trend could arise out of high mobility of TBZT, which could localize the electron density
TBZT S - 2p
0.49 eV
Partial TBZT
1.11 eV
0.8
GBZT
the XPS and UPS studies. We have shown the effect of 2,5 – dibenzthiazolyl
properties of GBZT.
V. VIII: References:
2. Rafal Dylemicz, Seqiusz Z. Patela and Regina Paszkiewicz, Proc. SPIE Int. Soc.
4. C. Baker, I.S.Gregory. W.R.Tribe, I.V. Bradley, M.J. Evans, E.H. Linfield, and
5. J. Kido, K. Hongawa, K.Okuyama and K. Nagai, Appl. Phys. Lett, 64, 815, 1994.
86, 4076,1999.
7. Y. He, S. Gong, R. Hattori, and J. Kanicki, Appl. Phys. Lett, 74, 2265, 1999.
131
8. T. P. Nguyen, P. Jonnard, F. Vernard, P. F. Staub, J. Thiion, M. Lapkowski, V. H.
10. X. H. Zhang, O.Y. Wong, Z.Q.Gao, C.S. Lee, H.L. Kwong, S.T. Lee and S.K.
12. P.E. Burrows, L. S. Sapochak, D.M. McCarty, S.R. Forrest, and M. E. Thompson,
13. Jason D. Slinker, Alon A. Gorodetsky, Michael S. Lowry, Jingjing Wang, Sara
600
800
400
500
1.0
0.0
0.2
0.4
0.6
Parker, Richard Rohl, Stefan Bernhard, and George G. Malliaras, J Am. Chem.
15. H. Ishii, K. Sugyama, D. Yoshimura, E. Ito, Y. Ouchi and K. Seki, IEEE J. Sel.
132
Summary and conclusions
133
First report on thiophene based benzthiazole molecule for the use in electron
transport layers, which has the mobility, 3 – 6 X 10-4 cm2/Vs, two orders of
magnitude higher than the well-known Alq3, characterized by photo generated
time of flight mobility measurements.
benzthiazole molecule, which shows promise for the use in white light emitting
and as good transport layers in light emitting diodes. Some of the issues like the
example ZBZT and GBZT which shows broad light emissions irrespective of their
explore new molecules for the use in light emitting diodes we have synthesized
TBZT as one of the candidate, which has superior properties than AlQ3 in terms
of electron mobility.
134
Appendix V - 1
The experimental investigations underlying XPS and UPS were to predict the HOMO
level and ionization potential of the GBZT complex and to investigate the interfacial
energy alignments in the device structures. First we show the investigations on the
analysis was done to predict the HOMO level of the GBZT by depositing on the Au
substrate. For the investigation of interfacial properties between GBZT and TPD in
absence of any active substrate like ITO etc. For this purpose we carried out sequential
After each deposited layer we carried out insitu XPS and UPS analysis. Thicknesses of
the layers were insitu monitored by quartz thickness monitor. The energy scale for XPS
was calibrated to reproduce the binding energy (BE) of Au 4f7/2 (84.00 eV). Note that the
work function of the instrument was grounded to the work function of Au in all the
measurements.
Figure V. 5.5.1 shows the overview of the XPS spectra of all deposited layers in the
sequence Au/GBZT/TPD/Au. Insitu XPS studies were carried out with different thickness
deposition. As can be seen the peak around 86 eV, 335 eV which is assigned to Au – 4f,
coverage of GBZT on the Au surface. Peak at 285 eV became stronger with the
135
deposition of GBZT which is assigned as C – 1s peak position, which is highlighted in the
discussion of Figure V.5.5.5. With the subsequent deposition of TPD over GBZT, the
peak at 426 eV disappears which is due to the Auger – Ga, indicates the complete
coverage of TPD.
( e )
( d )
Auger-Ga
1/2
3/2
( c )
Ga - 2p
Ga-2p
N-1S
( b )
C-1s
7/2
Au-4f
( a )
5/2
3/2
Au - 4d
Au- 4d
0 2 0 0 4 0 0 6 0 0 8 0 0 1 0 0 0 1 2 0 0 1 4 0 0
B i n d i n g E n e r g y ( e V )
Figure V.A - 1.1: shows the XPS – overview spectra of (a) Au deposition (b)
GBZT (100Å) on Au layer (c) 240 Å GBZT on Au (d) TPD over layer on
GBZT/Au (e) Au deposited on TPD/GBZT/Au layers.
136
The peaks at 229 eV (S – 2s), 110 eV (Ga – 2p), 21.80 eV (Ga – 3d), 1116 eV (Ga – 2p1/2)
and 1144 eV (Ga – 2p3/2) also disappear as a consequence of TPD deposition. With the
partial coverage of Au on TPD the peaks at 85.9, 335, 354 eV, which are characteristic
of Au peaks, reappears.
Figure V. 5.5.2 show the valance band spectra of Au – GBZT and Au/GBZT/TPD.
The first HOMO level of GBZT was located at 0.81 eV below the Gold Fermi level, and
TPD first HOMO level is located at 2.01 eV below the Gold Fermi level. To determine
the ionization potentials of the GBZT and TPD in the device structure, it is essential to
have an idea about the vacuum level alignments in the device structure.
UPS
1.0
Au/GBZT
0.8
Intensity
0.6
0.4
Au/GBZT/TPD
0.2
0.0
-2 0 2 4 6 8 10
Binding Energy (eV)
137
Figure V.5.5.3 shows the low energy onset of the sequential layers using UPS
technique. ONSET spectra essentially give the relative position of vacuum level at the
interfaces. According to Schotky model the vacuum level will get aligned themselves
between the interfaces for an ideal interfacial barrier, i.e., with no interfacial dipolar
formation.
GBZT-TPD ONSET
Au-GBZT
Au
0.5eV
-1 -2 -3 -4 -5 -6 -7 -8
Binding Energy (eV)
Figure V.A – 1.3: shows the ONSET spectra of the Au/GBZT and
Au/GBZT/TPD interfaces. Note the formation of interfacial dipolar formation
between the Au and GBZT interface leading to an ONSET shift of 0.5 eV in the
vacuum level.
138
But in real cases they will be formation of interfacial dipolar between the
interface which leads to the change in the relative positions of the vacuum levels and
hence the ionization potentials in the device structure will be difference from the of the
As can be seen there is a shift in the onset spectra of the order of 0.5 eV between
the Au – GBZT interface which is due to the interfacial dipole formation between the
metal and organic interface. This difference is very marginal between the Organic –
Organic interface that is of the order of 0.09 eV in the present study. It is known in the
literature that the vacuum level shifts in case of M – O will be considerably high which is
Figure V.5.5.5 shows the XPS spectra of C – 1s with the sequential deposition of
GBZT, TPD and Au. The C – 1s peak undergoes a 0.5 eV shift to higher BE with the
first few angstrom (100Å) of GBZT deposition on Au surface and its position and
shape remain basically unchanged thereafter. The shift in the C –1s spectrum was
indicative of formation of interface dipole at the interface of Au and GBZT. All the
spectra are similar in shape with no substantial change in the peak broadness
0.23 eV also observed between the TPD and Au interface towards the lower energy
region.
139
TPD - Au C- 1s
0.23eV
GBZT-TPD
0.49eV
GBZT-Partial TPD
0.45eV
Au-Full GBZT
0.5eV
140
Appendix - 2
V. A .II.1: Introduction:
The motive behind the fabrication of TBZT lies on the fact that polythiophene
units which are known for their superior hole transport abilities are sensitive to the
substitution of hetero atoms like nitrogen and sulphur in the main chain and end capping
in controlling the transport properties. Based on this analogy, we have end - capped the
thiophene with benzthiazole group at both the ends [1,2]. First we show the synthesis and
X Y X
S S Y
Z Z
X Y X
S S S Y
Z Z
S
V. A .II. 2: Experimental:
were taken in a borosil beaker along with the calculated amount of poly phosphoric acid,
which acts as a solvent and acid catalyst. Use of polyphosphoric acid is recommended
since it is a good microwave absorber due to its high polarity, results in a superheating of
the system, giving good yields. Reaction was carried out in a microwave oven at a power
141
level of 20% of total 800 W at ambient conditions. The total reaction time was 12
minutes. After the reaction was over, the crude product was obtained by work up of the
reaction mixture with cold water. Subsequently the product was washed with dil. NH4OH
and recrystallized twice in hot toluene. Yield: 84%. m.p. 145 - 150oC. 1H-NMR (400 M
Hz) – (t, 7.5243, J 4.06 Hz), (t, 7.6035, J 3.96 Hz), (d, 8.0869, J 4.99Hz), (d, 8.187, J 4.95
Hz), (s, 7.974) IR – (cm-1) – 3059.32, 1593.78, 1426.16, 1307.65, 914.94, 796.24,
S – 27.44%. Note that the synthesis of TBZT can be carried out using conventional oil
using SCE as standard electrode and Pt as the working electrode in 0.001M tetra butyl
ammonium per chlorate electrolytic conditions. Cyclic voltammogram shows two fully
transfer steps, indicating the ability of the molecule to undergo reduction easily, making
it a good electron transport material. This can be understood by the fact that the
introduction of heteroatom in the system, which suppresses the oxidation of the system as
reported for the oligothiophene systems, promotes the reduction pathway of the
molecules [1,2].
Time of flight measurements were carried out using frequency tripled Nd – YAG
laser ( = 355 nm, = 6 ns, 2 Hz) with incident power of 5 mJcm-2. Figure V.A – 2.2.
142
shows the current transient for ITO/TBZT (1.2~1.7µm)/Al (100nm) device as a function
of time under forward bias conditions for a specific carrier mobility. Under these
conditions, photo generation is confined to a layer (a few 100 nm thickness) close to the
ITO electrode. An optical pulse incident on the material through the transparent anodic
contact creates a thin sheet of electron – hole pairs next to the contact. The absorption
depth of the optical excitation is small compared to the film thickness and the optical
pulse duration is short compared to the transit time of the charge carriers across the
sample.
Low intensity optical pulses were used so that the photo generated charge carrier
density does not significantly perturb the spatially uniform electric field in the structure,
i.e. TOF measurements were performed in the quasi space – charge – free conditions. The
µe = d/ E -------------------------- (1)
where is the transit time of the carriers, d is the film thickness (1.7 m), and E is the
applied voltage (2.5 x 105V/cm). It can be seen that there is an initial current peak at
short times, commonly attributed to an initial relaxation of the charge carriers towards
their intrinsic density – of – states distribution [3,4]. For dispersive transients, where
inflection point is not visible, ttr is taken at the point of intersection of the linear
asymptotes [5,6]. Figure V.A – 2. 3 shows the electron mobility as a function of electric
field determined from the TOF measurements and a least square fit (solid line) to the
mobility. The field dependence of the mobility provides information about the carrier
143
2E-4 ITO/TBZT(1.2 ~ 1.7µm)/Al (100nm)
C u r r e n t (a . u)
2E-5
2E-6
Figure V.A – 2. 2: Time - of - flight photo current transient for ITO/ 2,5 –
dibenzthiazolyl thiophene / Al shows dispersive transients. Note that transit time, ttr
was taken at the point of intersection of the linear asymptotes.
1E-5
Mobility (cm2/Vs)
1E-4
1E-3
0.01
450 500 550 600 650 700 750
1/2 1/2
E (V/cm)
Figure V.A – 2. 3: Experimental field dependence of electron mobility, solid
line shows best Poole – Frenkel fit.
144
Values of µe computed from Eq. (1) are plotted against E1/2. All the data can be fitted to a
where β is the PF slope. The error bars on the mobility shown in the inset to Figure V.A
– 2. 3 are estimates from TOF measurements on several different devices. As can be seen,
µe has relatively weak field dependence and has a value between 3 – 6 x 10 –4 cm2 V-1s-1
in the field range 450 < E0.5 < 700 (V cm-1) which is equivalent to the commonly used
Theoretical studies have shown that such weak field dependence is characteristic
of a system with little geometrical flexibility [8,9]. To find out the structural rigidity we
carried out AM1-CI calculations on the neutral and anionic species of TBZT, which show
that there is a strong electron delocalization in the ground and excited states making the
molecule rigid under the photo - excited conditions in the anionic form. Figure V.A – 2.
4 shows the electron density mapping of HOMO, LUMO levels of the molecule, which
shows that the total energy of the system in the anionic form is strongly dependant on the
torsional angle. For neutral TBZT, the total energy is almost independent of the torsion
angle.
The mobility value of TBZT is high compared to that of the conventionally used
Alq3, which has a value of 1.4 x 10-6 cm2/Vs, hence TBZT can be used as an effective
145
LUMO
HOMO
0.010
0.008 3.5 V
Current (Amp )
0.006 Al
TBZT
TPD
0.004
ITO
0.002
0.000
0 1 2 3 4
Vo l t a g e ( Vo l t s )
Figure V.A - 2.5: Current – Voltage characteristics of bi - layer device,
ITO/TPD/TBZT/Al showing a threshold voltage of 3.5 V.
146
electron-injecting layer compared to the Alq3 to carry high current at low voltage.
showing low threshold voltage of 3.5 V with high current output values. The schematic of
the device is shown as an inset to Figure V.A - 2.5 where in TPD is used as a hole
transport layer and TBZT as an electron transport and emissive layer. The device
structure does give high current values but doesn’ t emit appreciable light out put at
various thicknesses. One of the possible reasons is that the recombination zone of the
light emission is moved to the anodic region owing to the high mobility value of TBZT.
hydroxyl phenyl) benzthiazolate) Zinc (II) complex ) acts as an electron transport and
unusually broad band emission with a full width half maxima of more than 220 nm (filled
energies were attributed to the formation of exciplex at the interface of TPD and ZBZT
much narrowed emission (open symbols) with a FWHM of 190 nm and a large drop in
characteristics can be attributed to the presence of TBZT layer in the device structure.
Owing to its high electron mobility, TBZT brings the recombination zone away from the
147
interface reducing the effect of exciplex to cause the narrowing of the emission spectra.
This confirms the electron transport capability of TBZT in the device structures.
ITO/TPD(50nm)/ZBZT(80nm)/TBZT(10nm)Al
1.0
0.8
Electroluminescence
0.6
0.4
0.2
ITO/TPD (50nm)/ZBZT( 80 nm) /Al
0.0
400 450 500 550 600 650 700 750
Wa v e l e n g t h ( n m )
Figure V.A - 2.6: shows the effect of TBZT on the ZBZT electroluminescent properties
using the device structure ITO/TPD/ZBZT/Al.
V. A.II. 5: References:
2153, 1999.
2. J. Caldas, E. Pettenati, G. Goldoni, and E. Molinari, Appl. Phys. Lett. 79, 2505,
2001.
4. E. Muller – Horsche, D. Haarer, and H. Scher, Phys. Rev. B 35, 1273, 1987.
148
5. I. H. Campbell, D.L. Smith, C.J. Neef, and J.P. Ferraris, Appl. Phys. Lett. 74,
2809, 1999.
8. Z.G. Yu, D.L. Smith, A. Saxena, R. L. Martin, and A.R. Bishop, Phys. Rev. Lett.
1774/DEL/2004.
149