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Study of optical and electroluminescent properties of conjugated polymers
VIETNAM NATIONAL UNIVERSITY, HANOI COLLEGE OF TECHNOLOGY
DO PHUONG ANH
STUDY OF OPTICAL AND ELECTROLUMINESCENT PROPERTIES OF CONJUGATED POLYMERS
THESIS FOR THE DEGREE OF BACHELOR OF SCIENCE IN TELECOMMUNICATIONS
Supervisors:
Assoc.Prof.Dr. Nguyen Nang Dinh
HANOI - 2005

ABTRACT
This diploma work presents study of electrical, optical, electro- and photoluminescent properties of some polymers included conjugate polymer like MEH-PPV. To prepare organic light-emitting diodes (OLEDs) the following techniques have been used: Electron beam deposition for transparent electrically conducting ITO films (used as anode) Spin coating method for PVK (used as hole transport layer) and MEH-PPV (as emitter) Vacuum evaporation for Alq3 (as emitting material) and Ag, Al films (as cathode) To characterize materials and devices the following methods have been used: Micro Raman for study of molecular structure of the polymers SEM for study of surface morphology Electrical and spectroscopic measurements for study of I-V, electroluminescent (EL), photoluminescent characteristics of the organic light-emitting diodes . From experimental results we showed that both the electrical and electroluminescent properties of the devices with addition of the hole transport layer and the electron transport layer have been considerably improved: Onset voltage of ITO/PVK/MEH-PPV/Ag is lower than the one of ITO/MEH-PPV/Ag. For the full layer device like ITO/PVK/Alq3/LiF/Al where there are both the hole transport layer and the electron transport layer, I-V and pholtoluminescent characteristic have been much enhanced. Finally, a nanostructured composite film of PVK + nc-TiO2 has been studied. The results obtained showed that photoluminescent behaviour of the nano2

composite was quite different than for a standard PVK film: the photoluminescent intensity of the nanocomposite was increased nearby one order in magnitude.

INTRODUCTION
Organic electroluminescence (EL) is the electrically driven emission of light from non-crystalline organic materials, which was first observed and extensively studied in the 1960s. In 1987, a team in Kodak introduced a double layer organic light-emitting device (OLED). The advance in OLEDs has led to its application to flat panel displays. The promise of low-power consumption and excellent emissive quality with a wide viewing angle is unique among display technologies. At the moment, passive monochrome and multicolor displays are commercially available, and active-matrix full-color displays have been demonstrated. In comparision with technology for inorganic LED, the technology for OLEDs is much simpler and easier. With the aim to study electro- and photo luminescent properties of some conjugated polymers. We have carried out preparation and characterization of two types of OLEDs such as ITO/PVK/MEHPPV/Ag and ITO/PVK/Alq3/LiF/Al. To search new photoluminescent materials used for luminescent devices a nanostructured composite film of PVK+nc-TiO2 has also been studied. Thus, the title Study of optical and electroluminescent properties of conjugate polymers , the references. thesis consists of four chaptes, conclusion and

CHAPTER I. OVERVIEW OF CONDUCTING POLYMERS THE BASIC CONCEPT
For recent years, conducting polymers are regarded as synthetic metal because they have the electrical, electronic, magnetic and optical properties of metal. They are synthesized by doping an organic polymer, either an insulator or semiconductor. After doping, electric conductivity of polymers can increase as many as 105 times. So their conductivities are in the metallic conducting range (from 1 to 104 s/cm). Since the initial discovery in 1977 that polyacetylene (CH)x now commonly known as the prototype conducting polymer, the development of the field of conducting polymers is forecast to rise steadily. Today, the researching tend is concentrating in other types of conducting polymers and their derivatives. Such as PPV (poly 1,4-phenylenevinylene), PVK (poly N-vinylcarbazole) those conducting polymers showed us promising prospects not only on studying scientific but also in practical applications. They created a number of opportunities: Conducting polymers opened the way to progress in understanding the fundamental chemistry and physics of -bonded macromolecules. Conducting polymers provided an opportunity to address questions that had been of fundamental interest to quantum chemistry for decades: Is there bond alternation in long chain polymers? What is the relative importance of the electron-electron macromolecules? And perhaps most important conducting polymers offered the promise of achieving a new generation of polymers: Materials which exhibit the electrical and optical properties of metals or semiconductors and which retain the attractive mechanical properties and processing advantages of polymers. 5 and the electron-lattice interactions in -bonded

1.2. THE CLASSIFICATION
Today, many different kinds of conducting polymer were made. To classify, one should depend on their structure and mechanism doping. Reversible doping of conducting polymers, with associated control of the electrical conductivity over the full range from insulator to metal, can be accomplished either by chemical doping or by electrochemical doping. Concurrent with the doping, the electrochemical potential (the Fermi level) is moved either by a redox reaction or by an acid base reaction into a region of energy where is a high density of electronic states; charge neutrality is maintained by the introduction of counter ions. Metallic polymers are, therefore, salts. The electrical conductivity results from the existence of charge carriers (through doping) and from the ability of those charge carriers move along the - bonded highway. Charge injection onto conjugated, semiconducting macromolecular chains, doping, leads to the wide variety of interesting and important phenomena which define the fields. Reversible charge injection by doping can be accomplished in a number of ways:
1.2.1. Chemical doping by charge transfer

The initial discovery of the ability to dope conjugated polymers involved charge transfer redox chemistry; oxidation (p-type doping) or reduction (n-type doping) [1], as illustrated with the following examples: p-type:
( polymer )
n-type:
+ 3 / 2ny ( I 2 ) ( polymer )
+Y
(I ) ]
3
y n
(1)
( polymer)n + [Na+ (Napthtalide) ]y [(Na+ )y ( polymer) y ]n + (Naphth)o

metal.
(2)
When the doping level is sufficiently high, the electronic structure evolves to that of
Fig.1. Doping mechanisms and related applications
1.2.2. Electrochemical doping Although chemical (charge transfer) doping in an efficient and straightforward process, it is typically difficult to control. Complete doping to the highest concentration yields reasonably high quality materials. However, attempts to obtain intermediate doping levels often result in inhomogeneous doping. Electrochemical doping was invented to solve this problem [2]. In electrochemical doping, the electrode supplies the redox charge to the conducting polymer, while ions diffuse into (or out of) the polymer structure from the nearby electrolyte to compensate the electronic charge. The doping level is determined by the voltage between the conducting polymer and the counter - electrode; at electrochemical equilibrium the doping level is precisely defined by that voltage. Thus, doping at 7

any level can be achieved by setting to come to electrochemical equilibrium (as indicated by the current through the cell going to zero). Electrochemical doping is illustrated by the following examples: p-type:
( polymer )n + [Li + (BF4 )]sol 'n [( polymer )(BF4 )y ] n + Li(electrode)

n-type:
(3)
( polymer )n + Li (electrode) [(Li + )y ( polymer ) y ]n + [Li + (BF 4 )]sol 'n

1.2.3. Doping of polyaniline by acid-base chemistry
(4)
Polyaniline provides the prototypical example of a chemically distinct doping mechanism. Protonation by acid - base chemistry leads to an internal redox reaction and the conversion form semiconductor (the emeraldine base) to metal (the emeraldine salt). The doping mechanism is schematically in Fig.2. The chemical structure of the semiconducting emeraldine base form of polyaniline is that of an alternating copolymer. Upon protonation of the emeraldine base to eth emeraldine salt, the portion induced spin unpairing mechanism leads to a structural change with one unpaired spin per repeat unit, but with no change in the number of electrons. The result is a half-filled band and, potentially, a metallic state where there is a positive charge in each repeat unit (from protonation) and an associated counter ion (e.g. Cl , HSO4 , DBSA etc; the counter ion is not shown in Fig.2). This remarkable conversion from semiconductor to metal has been well described, but it is not well understood from the view of basic theory. There are no calculations which show that the metallic (emeraldine salt) final state is lower in energy than the semiconductor and no detailed understanding of the rearrangement reactions sketched in Fig.2.
Fig.2. Protonation induced spin unpairing in polyanline; conversion from insulator to

metal with no change in the number of electrons
1.2.4. Photo-doping
The semiconducting polymer is locally oxidized and (near by) reduced by the photo-absorption and charge separation (electron hole pair creation and separation into free carriers):
( polymer )n + h [{ polymer}+ y + { polymer} y ]n
(5)
Where y is the number of electron hole pairs (dependent upon the pump rate in competition with the recombination rate). The branching ratio between free carriers and bound exciton (and the closely related issue of the magnitude of the exciton binding energy) is a subject of continuing discussion. Following photo-excitation from the ground state (1 Ag in the notation of molecular spectroscopy) to the lowest energy state with proper symmetry (1Bu), recombination to the ground state can be either radiative (luminescence) or 9

nonradiative. Some families of conjugated polymers exhibit high luminescence quantum efficiencies (for example, PPV and PPP and their soluble derivatives); others do not (for example, polyacetylene and the polythiophenes). A number of mechanisms have been identified that lead to low quantum efficiencies for photoluminescence. Rapid bond relaxation in the excited state and the formation of solutions with states at mid gap prevent radiative recombination in polyacetylene [3]. The existence of an Ag state or a triplet excited state below the 1Bu state will favor nonradiative recombination (in both case, direct radiative transitions to the ground state are forbidden). Interchain interactions in the excited state (excimers) also lead to nonradiative channels for decay.
10

Fig.3. Molecular structures of a few conjugated polymers
CHAPTER II. ORGANIC LIGHT-EMITTING DIODE (OLED) 2.1. INTRODUCTION

Electroluminescence is the light emitted by a solid through which an electric current is passing, in addition to its normal thermal emission. It implies the presence of electronic excited states with populations larger than their thermal equilibrium value. Organic electroluminescence (EL) is the electrically driven emission of light form non-crystalline organic materials, which was first observed and extensively studied in the 1960s [4]. In 1987, a team in Kodak introduced a double layer organic light-emitting device (OLED), which combined modern thin film deposition techniques with suitable materials and structure to give moderately low bias voltages and attractive luminance efficiency. Since then, there have been creasing interests, research activities in this new field and enormous progress has been made in the improvements of color gamut, luminance efficiency and device reliability. The growing interest is largely motivated by the promise of the use of this technology in flat panel displays. As a consequence, various OLED displays have been demonstrated. The design of EL materials for used in OLEDs is critical to device performance. Great strides have been made towards the development and improvement of molecular materials for display applications. The most critical performance characteristic for OLEDs is the device operational lifetime. Continuous operation of OLDEs generally leads to a steady loss of efficiency and a gradual rise in bias voltage. Although OLEDs have achieved long operational stability, the material issues underlying the EL degradation are not fully understood. The remarkable advance in OLEDs has led to its application to flat panel displays. The promise of low-power consumption and excellent emissive quality 11

with a wide viewing angle is unique among display technologies. At the moment, passive monochrome and multicolor displays are commercially available, and active-matrix full-color displays have been demonstrated.
2.2. DEVICE CONFIGURATION

An OLED has an organic EL medium consisting of extremely thin layers (<0.2 m in combined thickness) sandwiched by two electrodes. In a basic twolayer OLED structure, one organic layer is specifically chosen to transport holes and the other organic layer is specifically chosen to transport electrons. The interface between the two layers provides an efficient site for the recombination of the injected hole-electron pair and resultant electroluminescence. When an electrical potential difference is applied between the anode and the cathodes such that the anode is at a more positive electrical potential with respect to the cathode, injection of holes occurs from the anode into the hole-transport layer (HTL), while electrons are injected from the cathode into the electron-transport layer (ETL). The injected holes and electrons each migrate toward the oppositely charged electrode and the recombination of electrons and holes occurs near the junction in the luminescent ETL. Upon recombination, energy is released as light, which is emitted from the light-transmissive anode and substrate. Charge injection and transport are the limiting factors in determining operating voltage and luminance efficiency. In OLEDs, the hole current is limited by injection, and the electron current is strongly influenced by the presence of traps owing to metal-organic interactions. In order to enhance carrier injection the selection of efficiently electron-injecting cathode materials and the use of appropriate surface treatments of anodes are of great importance. The efficiency of an OLED is determined by charge balance, radiative decay of excitons, and light extraction. Significant progress has been made recently in developing phosphorescent emitters via triplet-triplet energy transfer, and high-efficiency OLEDs in various colors have been demonstrated. Light extraction is determined by the device structure and the refractive indices of the composed layers. Current 12

research activity is directed toward various surface modifications that can increase extraction efficiency, while the problem of light-trapping remains unsolved in terms of its application to displays. The heterojunction should be designed to facilitate hole-injection from the HTL into the ETL and to block electron injection in the opposite direction in order to enhance the probability of exciton formation and recombination near the interface region. As shown in Fig.4, the highest occupied molecular orbital (HOMO) of the HTL is slightly above that of the ETL, so that holes can readily enter into the ETL, while the lowest unoccupied molecular orbital (LUMO) of the ETL is significantly below that of the HTL, so that electrons are confined in the ETL.
Fig.4. Energy level diagram of a two layer OLED
The low hole mobility in the ETL causes a build up in hole density, and thus enhance the collision capture process. Furthermore, by spacing this interface at a sufficient distance form the contact, the probability of quenching near the metallic 13

surface is greatly reduced. The simple structure can be modified to a three-layer structure, in which an additional luminescent layer is introduced between the HTL and the ETL to `function primarily as the site for hole-electron recombination and thus electroluminescence. In this respect, the function of the individual organic layers is distinct and can therefore be optimized independently. Thus, the luminescent or recombination layer can be chosen to have a desirable EL color as well as high luminance efficiency. Likewise, the ETL and the HTL can be optimized primarily for the carrier-transport property. The extremely thin organic EL medium offers reduced resistance, permitting higher current densities for a given level of electrical bias voltage. Since light emission is directly related to current density through the organic EL medium, the thin layers coupled with increased charge injection and transport efficiencies have allowed acceptable light emission to be achieved at low voltages.
2.3. THE OPERATION

It is convenient to consider the overall operation of an OLED as a sequence of 5 steps: charge injection at the electrodes, transport through the structure, recombination into a neutral excited state, emission of photon, transport of the photon out of the diode, as shown on Fig.5.
14

Fig.5. Schematic drawing of the five elementary steps of EL
15

2.3.1. Injection
The equilibrium concentrations of carriers in the organic materials used are very small: the forbidden gap is large, and shallow donors or acceptors are absent. The carriers present in the operating OLED must be injected from the electrodes. Generally, the relative positions of the energy levels in the organic film and the metal electrode are such that there is an energy barrier for injection. Injection may either proceed over the interface barrier by tunneling [5]. A problem that has been much neglected in OLEDs is carrier extraction: any injected carrier that has not recombined with a carrier of the opposite sign must eventually leave the film at the other electrode. If the recombination efficiency is not large, for instance if the electron and hole densities are very different, so that most of the majority carriers cannot recombine, their extraction may limit the current, thus leading to poor diode performance. However, accumulation of a large majority carrier density at the minority carrier injection electrode leads to a large potential difference buildup, hence a large minority current increase, a smaller current imbalance, and large efficiencies. Such processes may explain the successful operation of symmetrical ITO/Anthracene/ITO diodes or the possibility of using ITO as a cathode. Indeed, since ITO is a wide gap semiconductor, hole conducting levels of most OLED materials fall in its forbidden gap, which is not favorable for fast extraction. If a large enough ensues, electrons may be field injected from ITO, despite the unfavorable positions of energy levels at equilibrium. In fact, this is the basis of current multiplication that has been observed in some organic photo conducting films. Therefore, injection and extraction are not unrelated. This is the first example of the interrelation of different elementary processes, which complicates a thorough treatment of organic EL.
2.3.2. Carrier transport

Once an electron and a hole have been injected, they must be transported 16

through the film to the point where they will recombine. In the organic films used in OLEDs, carrier transport is believed to be always by hoping between localized states. These excited states are usually loosely referred to as polarons, because some lattice relaxation around the charge is expected, but this does not imply any kind of coherent transport; chemists would merely speak of radical inons, polaron formation then meaning only that the neutral ground state and ion geometries are somewhat different. The formation of doubly charged species in doped conjugated polymers has been assumed, the socalled bipolarons [6], but there is no convincing evidence that they play a role in OLEDs
2.3.4. Carrier recombination

The dielectric constant of the organic materials used is always small (typically ~ 3-4), so Coulomb screening is inefficient and the distance:
rc = e2 4 0 kT
(6)
at which the attractive interaction between an electron and a hole is > kT, is large, typically 15nm at room temperature. The capture then results from a process of diffusion in a field, as in the case of weakly ionized dense gases treated long ago by Langevin, hence the name of Langevin recombineation used for this process. Hence large capture cross section ( rc ~ 10-11 cm2) and large recombination rate constants obeying the relation:
r =
e( + + )
(7)
independent of any applied field. This has been well established experimentally in the case of molecular crystals, and this is quite different from the case of semiconductors. The large recombination efficiency precludes the formation of injected plasma and in fact this is a strong point in favor of OLEDs. The theory describes the carrier approach very well, but says nothing about 17

the final recombination step itself. Implicit in the above is the assumption that it proceeds instantaneously once the carriers are on the same site. This has been hotly debated, at least for conjugated polymers. It seems now well established that in small molecules as well as in conjugated polymers, recombination produces a neutral excited state in the literature as an exciton, although a true exciton is a collective excitation of a periodic solid. During the lifetime e the exciton may be redissociated into a free carrier pair. The probability of redissociation depends on e and on the binding energy Eb (the difference between its energy and that of a free electron hole pair) of the exciton, which depends on the electric field at the exciton position. Be at zero field is usually quite large for molecular exactions, several tenths of an eve, up to 1 eV, for singlet exactions - and much larger for triplets - ; the situation in conjugated polymers has been less clear, Be is accurately known in polydiacetylenes only, Eb ~ 0.5 eV for the singlet, and this is expected to be a typical value; for instance, in PPV, the most studied EL conjugated polymer emitting in the green, the generally accepted value is Eb ~ 0.7 eV. Such a binding energy, together with an exciton lifetime ~ 1ns, leads to negligible redissociation at room temperature. However, in an applied electric field E, the barrier is depressed by an amount proportional to exp(E1/2), the so-called field-assisted dissociation. Evidence of this process has been observed in OLED films at high fields ~ 1MV/cm, i.e. 10V applied to 100 nm thick film. This leads to a decrease in recombination efficiency, and in EL field, at high fields. The Langevin recombination model does not take electron spin into account. Since e is very large, spin dependent (exchange) interactions would indeed certainly be negligible, but there is up to now no direct proof for this. However, the electron spin has consequences on the final neutral excited states produce.
2.3.4. Photon emission

Almost all organic materials used in OLEDs are composed of light elements only, mainly C and H; so, spin-orbit coupling effects are inefficient, and neutral excited states are well classified as singlet 18 (S=0) and triplets (S=1),

according to their spins and multiplicity; higher spin states are generally at too high energies to play any role here. The singlet-triplet energy splitting is large (typically 1 eV) The fact that electron and hole have initially no spin correlation, and the weakness of electron-hole magnetic interaction at large distance, naturally lead to the assumption that the exaction states are populated by recombination in proportion of their multiplicities: 4 recombining electron whole pairs yield 3 triplets and 1 singlet. If the quantum yield for singlet emission, the fluorescence, is s, and the one for triplet emission, the phosphorescence, is t, then the electroluminescence quantum yield is proportion to:
= s + 3 t
4
(8)
2.3.5. Photon extraction

This last step may have a large influence on the external yields. The emitting layer being generally disordered and non textured, the emission is isotropic inside the film, leading to an approximately Lambertian emission pattern outside the diode that is a luminance that is independent of the angle of view. For display applications this is indeed advantageous.
2.4. THE PARAMETERS

The internal quantum yield iq: is the ratio of the number of generated photons to the number of charges transport through the device. The internal energetic yield ie (in W/W): is the ratio of energy generated as light (radiant energy) to expended electrical energy, so it is smaller than the quantum yield by a factor h/eV. The corresponding external yield eq and ee refer to photons that are emitted in the outer space, and are smaller by the factor P0. However, these yields are not a number characteristic of a device; they depend on the operating conditions of the device, particularly the applied voltage. The luminous efficiency (lumen per watt) is the photometric equivalent of the external energetic yield weighted by a standard spectral function V() 19

representing the eye response. The lumen (lm) is the unit of luminous flux, the radiant flux weighted by V(). Finally another photometric quantity of importance is the luminous flux per solid angle unit (the candelea, cd = lm/sr). Taken per unit emitting surface, one gets the luminance (unit the cd/m2). Quantities of practical significance are the luminous efficacy (lm/W) and the luminance L (cd/m2), governed by ee. The internal quantum yield is the fundamental quantity of interest for the basic physical description, and its optimization leads to that of other quantities, depending on the understanding and control of the elementary steps of the EL process. The recombination of the minority carriers current Jmin, so the number of recombination events per second is e-1 r Jmin , where r is probability of recombination. To get the number of emitted photons, this number is to be multiplied by (e + 3 t)/4, or if the singlet exciton is the only radiant state by 0.25 s. The number of charges crossing the film is e-1Jtotal (the total current). The internal quantum yield iq is then:
iq =
( + 3 t ) J min r s J total 4
(9)
2.5. CURRENT LIMITING FACTORS 2.5.1. Current limiting factors

The current through the diode can be limited by the injecting capability of the electrode, in other words its saturation current. If this current is large enough another limitation appears, that of the total charge present in the bulk of the film, leading to a space charge limited current. Which one is limiting depends both on the carriers transport properties and on the injection conditions at the electrode. Consider first the simple case where only one electrode injects carriers; then all carriers in the film are of the same sign, and the current is limited by their space charge. Qualitatively, without going into the detailed theory, this charge is of the order of that of the corresponding capacitor:
20

Q
0 V
e D
(10)
D is the film thickness and the dielectric constant of the medium. If all charges are mobile, their motion in the average field V/D generates a current:
J 0
V 2
D3
(11)
The exact result differs from (11) by a factor 9/8 only. If a fraction of the charges is immobilized (trapped), the observed current is smaller and its V and D dependences may be steeper. Because trapped charges still take a part in the recombination, if not in transports; the corresponding rates are still given by equation (6) with the appropriate = 0, so a free-trapped recombination may be almost as efficient as a free-free one. This is largest unipolar current that can flow through the organic film for a given V. If the injecting electrode cannot supply that current, the actual J is smaller and determined by the electrode (injection limited). If the two types of carriers are present, their respective space charges compensate at least in part. The corresponding bipolar current may become larger than predicted by equation (11). In the absence of recombination, J may be increase very much. However, recombination is very efficient in organic materials, so bipolar injection currents are limited by a combination of space charge and recombination. The theoretical problem has been solved in the frame of the socalled simplified theory used to derive the V2D-3 law as in equation (11), leading to the same current voltage relation, but with a effective mobility depending on a complicated way on the microscopic mobility of each carrier and on the recombination rate constant r . To maximize the radiant flux, under a given applied voltage V, Jmin must be maximized, and maximizing iq implies a blanced bipolar injection. Equivalently, if such conditions are met, a given luminous efficiency will be achieved at the 21

smallest possible V. That is the highest possible ratio h/eV, optimizing the luminous efficiency and luminance. Under these conditions, J is proportional to . For maximum luminance under a given applied voltage, one should then have the largest possible . For a good emitting material with a small , more complicated device structures such as multiplayer diodes must be designed. 2.5.2. Unipolar bulk limited (space charge limited) current An important parameter in determining the EL yield is the probability of recombination of a minority carrier. It may depend on the applied voltage V, the injection conditions, transport properties and internal structure of the diode (monolayer or multilayer). Suppose that the majority carrier (labeled below) current is space charge limited and that the minority carrier (labeled below) density is small enough not to significantly perturb these SCL conditions. For simplicity, we neglect trapping and replace the actual, position dependent. So carrier density n and electric field E by their space averaged values: (a)
n =
3 0V , 2eD 2
(b) E =
V D
(12)
Using the equation (2) for the recombination rate constant of carrier, the average recombination lifetime of minority carrier r ( ) is:
r ( ) =
1 2 L2 = r n 3( + )V
(13)
To be compared to the transit time t ( ) :

L2 t ( ) = = E V L
(14)
The ratio:
22

( ) 2 r= r = 1 + t ( ) 3

1
(15)
gives an idea of the efficiency of the recombination process. If r = 1, half of the carriers recombines. We propose several conclusions follow: r < 2/3 always, so recombination is always efficient, this is a consequence of its Langevin character. If the minority carrier mobility is small ( / >> 1 ) recombination is complete, whatever the actual mobility. On the other hand, a large ( ) means a large value of r so recombination remains efficient. The recombination yield is not very dependent on the transport properties. If / 1 (Anthracenes case) recombination proceeds throughout the film volume. If / >> 1 recombination is limited to a layer of thickness w ~ 2D/3( / ) near the injecting contact or if surface quenching of the exitons is efficient, this may be a problem. The ratio is independent of D and V. In this case, the variation of EL quantum yield with V will reflect the V dependence of the minority carrier injection efficiency.
2.5.3. Double injection (bipolar) bulk limited current

The case treated above is the one in which the minority current is injection limited and small. The opposite limit is that of bulk-limited double injection. The injected current in the frame of the simplified theory and neglecting trapping effects, is:
J 0 eff V
2
L3
(16)
eff is in general a complicated function of the s. The theory has now been
explicitly applied to OLEDs. In the Langevins case, if the two mobility are equal (to ), one finds eff 2.88 and if one mobility is much larger than the other, for 23

instance h >> e , eff h or if recombination coefficient is given by Langevin formula, the double injection current is never much larger of the two possible unipolar SCL current. In other words, no injected plasma can be formed the double injection current is limited by a combination of recombination and space charge. The relative importance of these two factors depends on the position in the film. The above conclusions remain approximately valid. Indeed, they are supported by numerical calculations in the double injection case. 2.5.4. Electrode limited currents If the majority carrier current J is smaller than its SCL value, i.e. is injection limited, then n < n everywhere. So t ( ) is larger than the SCL value given in equation (2). The recombination efficiency at constant minority carrier current is smaller. In this case one may write:
J = e n V V2 << 0 3 L L
(17)
And the ratio of recombination time to transit time becomes:

J + J SCL
J 1 + J SCL
(18)
So, unless the mobility ratio / >> 1 , recombination is very inefficient. One easily understands that it is still possible to have total recombination of the minority carriers. It provided that their mobility is small enough compared to that of the majority carriers: If + >> , equation (5) becomes r e + / 0 and it not much affected by the small value of , while the electron transit time has become very long and if J / J SCL , recombination is very probable.
2.5.5. Thermionic injection currents in organic materials

The difference between semiconductors and organic solids may be expected here as well, based on their different transport properties. It may be useful to first 24

recall how the saturation injection current Jsat at a metal semiconductor interface can be obtained. Jsat is equal to the current Jth of thermal carriers crossing the interface from the semiconductor side:
J sat = J th = 1 1 enco th = e th N c exp 6 6 kT
(19)
nco is the carrier concentration in the conduction band of the semiconductor, th their
thermal velocity, Nc the conduction band density of states and =EC - EF the barrier height. Using for th and Nc the value for parabolic energy bands and the effective mass of carrier m* = m, one recovers the familiar relation:
J sat = AT 2 exp kT
(20)
with A = 120A/cm2K2 .If an externally applied voltage generates at the interface a field Ei, the existence of an image potential at the interface decreases the barrier
eE height by an amount = e 1 0
1/ 2
- the Schottky effect leading to a current
voltage relation:
J sat eE 1 / 2 i = AT exp exp kT 0 kT
2
(21)
this derivation implicitly assumes a large carrier mean free path (i.e. ballistic, not diffusive, transport). This criterion is far from been fulfilled in OLEDs. At a metal-organic interface, the image potential creates for the carrier a physical situation similar to that in the recombination event: diffusion in a field which now is 1D than 3D. Using again a detailed balance argument, J sat becomes equal to the recombination current at the interface for carriers coming from the organic side. So N c should be replaced by the density N s of sites accessible for transport in the organic material and the thermal velocity by the mobility. Recombination at an anthracene- electrolyte interface and saturation currents for injection by such as an interface has been shown to conform quite well to such a 25

model. The ideas have been recently applied to metal organic interfaces. J sat is still given by equation (15) but the constant is now much smaller. For instance, taking reasonable values such as N s = 1021 and = 10-5 cm2/Vs yields a constant smaller than 10-2A/cm2K2. This is very low value, leading to correspondingly smaller saturation currents and less efficient injection above the image potential barrier, is associated to the transport properties of the organic layer. But the image potential very close to the metal surface extends below its Fermi level. It has been pointed out that localized states within this region become charged by electron transfer from the metal. This immobile injected charge raises the top of the image potential barrier by up to several tenths of volts, further decreasing the injection efficiency.
2.6. MATERIALS
The materials using in OLEDs are divided into three types: hole injection and transport materials, electron injection and transport materials and emitting materials.
2.6.1. The organic emitting materials

The advantages of organic materials over inorganic materials are their excellent color gamut and high fluorescence efficiency. Light is produced in organic materials by the fast decay of excited molecular states and the color of light depends on the energy difference between those excited states and the molecular ground level. Many materials show intense photoluminescence with near unity quantum yield, while the EL efficiency is limited by the probability of creating non radiative triplet excited states in the electron hole recombination. Two types of OLED are usually considered differing by the nature of the active emitting material: either it consists of small conjugated molecules, often metal chelates such as AlQ3 (8-hydroxyquinoline aluminum) or of conjugated polymers such as PPV, PVK and their derivatives. Examples of molecular formulae are given in Fig.6 for both types of materials, choosing examples of 26

emitters in the blue, green, and red or red-orange. Conjugated polymers are reviewed in this issue by Martin et al. and by Marsitzky et al. From the point of view of physics one should rather consider the following two classes of materials. The conjugated entities are small, zero-dimensional (0D), and quite rigid. In the solid, they interact essentially via weak van der Waals forces; the solid is then only weakly anisotropic. This is the case of course of small molecules, but also of molecularly doped nonconjugated polymers (that is, containing a dispersion of fluorescent dye molecules) and (more important for OLEDs) of such polymers bearing conjugated side-group. The conjugated entities are one-dimensional (1D) polymer chains, entangled into an amorphous or at least highly disordered solid. In this case, intrachain interactions are typically 2 orders of magnitude stronger than inter-chain ones, which are of the Van der Walls type, and the solid may have locally very anisotropic properties. These two types differ electrically in their energy level schemes and transport properties.
27
Fig.6. Example of conjugated polymer, emitting in the blue (upper row), green (middle)
and red or red-orange (bottom)
In the 0D case, interaction energies are very small compared to electronic transition energies; the fluctuations of the latter in the solid, hence the energy spread of hole, or electron, conducting states remain small as well (a few tenths of eV at most). The gap between hole and electron conducting states is large and essentially empty (except for chemical impurities). In the 1D case, the situation is less clear. The large intra-chain coupling would generate, in a perfectly regular chain, 1D energy bands several eV wide. This is indeed observed in the only case where regular chains can be made, the polydiacetylenes. Many band structures of conjugated polymers have been calculated. Disorder strongly localizes the electronic states. This is often described by a simple model in which the extended conjugation of the perfect chain is broken 28

into shorter segments of various lengths. Each segment is then taken as a box and its excited states energies will be higher the smaller the box (the conjugation length model). The total energy spread of the assembly of disordered chains remains large, but most electron or hole states are localized and transport occurs by hoping between boxes. Although this picture is over schematic, certainly the states span a large energy range and most of them are localized. Because of this large width, the polymer situation differs somewhat from that of the small molecules. These differences will be of consequence for interface levels at the metal-organic interface, hence for carrier injection.
2.6.2. The materials for cathodes

Metal alloys and compounds are used for cathodes of OLED because thay 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.
a. Mg Ag metallic films
Mg Ag with a volume ratio of 10:1 is commonly used as a low work function electron injecting cathode on Alq3. The addition of Ag into Mg considerably improves its chemical stability in the atmosphere and increases its sticking coefficient onto Alq3 upon deposition.
b. Li Al films
It is low work function and considered as an effective cathode to achieve efficient electron injection in OLEDs.
c .LiF/Al films
The bilayer cathode (LiF/Al) has been applied to various organic materials to form an effective electron injector. For instance, a blue OLED with a LiF/Al cathode on an emissive/electron transport layer of 4,4- bis(2,2 - diphenylvinyl)1,1-biphenyl (DPVBi) had an external quantum efficiency of 1.4%, which 29

represented a 50 fold increase in the device efficiency compared to a device with an Al only cathode.
2.6.3. The materials for Anodes

The material for anode is widely ITO (Indium tin oxide). It is a degenerate n-type semiconducting material that has wide applications in optics and optoelectronics. These applications include flat panel display devices, heat reflecting mirrors, and heterojunction solar cells. High electrical conductivity ( 2 x 10-4 -1 cm-1) and high transparency ( 90% in the visible spectrum range) of this material have been the focus of research throughout the world. Most of the research on ITO thin films is concentrated on the simultaneous improvement of the conductivity and the transparency of the ITO thin films deposited on glass substrates by a variety of techniques such as sputtering, electron beam deposition and chemical vapor deposition. Although ITO has the virtue of optical transparency but it is not a well controlled material. Several alternative materials have been recently examined as anodes; however all suffer from some unfavorable characteristics.
2.7. DIFFERENT TYPES OF OLED 2.7.1. The single of OLED

The basic organic light-emitting diode is a Metal-Insulator-Metal diode working in the double injection regime that is with strongly hole-injecting anode and a strongly electron-injecting cathode. The applications considered for organic electroluminescence are mostly in display, from simple signs to large area TV screens. Their emission must be in the visible; a photon energy < 3 eV requires that the emitting materials be conjugated molecules or polymers. In such Ag PVK ITO Glass materials, the electron and the hole conducting levels will be typically 2-3 eV and 5-6 eV respectively below the
30
Fig.7. Structure of single OLED

vacuum level corresponding to the electron affinity and the ionization potential of the material.
The cathode and anode must inject into these levels. For thermionic injection to occur, the anode material should then have a large work function W. A convenient transparent anode, through which the emitted luminescence can leave the diode, is an ITO layer on glass, with W ~ 4.7 4.9 eV, depending on the surface treatment ITO. It is a degenerate n type semiconductor of high conductivity, with a gap larger than 3.5 eV. So it is transparent throughout the visible range. At the cathode for thermionic injection to be efficient, a low W metal is required but such metals are quite reactive, so the problem is not easily solved. Choice material are presently calcium (W = 2.87 eV) or Mg/Ag alloy (W = 3.66 eV for Mg). The energy levels in an OLED operating under forward bias and assuming thermionic injection at both electrodes, are usually drawn in the literature as on Fig.7. For several reasons, such a figure is illustrative only. The electron and hole conducting layers in the bulk are drawn as well defined and the internal electric field is assumed to be constant. Neither can be actually correct. This is not a single energy level such as the HOMO or LUMO of an isolated molecule: intermolecular interactions generate bands. But the organic layer is essentially amorphous and energy band tails should be presented. On the other hand, assuming that constant field amounts to neglect space-charge effects. They are almost always important in insulators and any localized level that could lead to Schottky barrier formation. In fact, evidence for Schottky barriers in OLEDs has remained scarce.
31
Fig.8.The simplest model of an OLED made of a single organic layer between two
injecting
At the interface, the relative energy level positions may be not be as show, the figure implies a negligible effect of interface states or layers. Also, electrodes may operate in other regimes than the thermionic injection one implied by the small contact barriers shown. Indeed, Al has been used quite often as a cathode, for instance in the first polymer LED made, despite its larger work function W = 4.2 eV. This suggests the presence of a barrier layer or interface states at the electrode. So, for single polymer layer devices there are two ways to optimize injection. The first is to select electrode materials with work-functions that match the electron affinity and ionization potential of the polymer layer. And the second, the converse, is to tune the polymer energy levels to match to the work-functions of electrode.
2.7.2. Multilayer diodes

In order to get good thermionic injection at both electrodes in a single layer divice, the organic material should have a large electron affinity Ac 3 eV and a small ionization potential I c 5 eV. These conditions are contradictory with the requirement that exiton emission should occur in the visible at 2.5 0.5 eV, as the exiton energy is the gap energy E g = I c Ac minus the exiton binding energy ~ 0.5 eV. One way around the difficulty is to modify the electrodes by suitable layers 32

and/or exploit nonthermionic injection processes. Another method is to decouple the conditions at the two electrodes by using a bilayer diode shown in fig.9 in which the material close to the cathode has a large Ac (and a large Ic) and the other a small Ic (and a small Ac). There is then an organic organic interface within the diodes, which is an internal barrier for at least one carrier. Suppose that both leakage currents over the barrier are small (this is the most frequent case). Then, the current in each layer is essentially unipolar and by continuity the currents must be equal. The electrical conditions in both layers must adjust so as to achieve this equality, whatever the injection and transport properties. For instance, if the layer thicknesses are comparable and both current are SCL, the field will be lower in the layer with the larger . If not all recombination events will occur near the barrier, away from the electrodes, there by minimizing exciton quenching at the electrodes.
Fig.9. A two layers diode under forward bias A bilayer diode seems then to have several advantages (Fig. 10). But of course a more complicated structure raises more complex optimization problems.
33

One can go further in specializing a layer in a single function, for instance, putting near the anode a layer adjusting the injection conditions (such as the conducting polymer PEDOT), the second layer with high h good at transporting holes. Then, a highly fluorescent layer where recombination will occur and two more layers are for electron transport and injection. The device may be further complicated by adding suitable Al Alq3 PVK ITO Glass dopants in one or several layers, mainly the emitting one in order to increase the yield or shift the emission wavelength. For instance, a combination of dopants emitting in different spectral ranges may be used to generate white light. As pointed out earlier, it is relatively easy to prepare multilayer with abrupt interfaces by vacuum Fig. 10. Structure of a multilayer OLED
sublimation, although subsequent annealing may lead to interdiffusion. But this is not so with spin coated polymer layers. Multilayer OLEDs of a mixed type, incorporating polymer and small molecules layers have been prepared but of course the simplicity of the spin deposition method is then lost. The main new physical problem introduced by multilayer is the presence of organic organic interfaces, which are still not well understood. The energy levels alignment at such interfaces is currently actively studied. There are two questions mentioned here. The first, an image potential also exists at such an interface, associated to the difference in the materials dielectric constant, generating a potential well. It may be 1 eV deep as in the Si-SiO2 case. It may be expected to be much shallower in OLEDs unless specifically chosen materials are used. But its presence may affect the recombination process significantly. 34

The second, the polymer polymer interfaces are quite different from those including small molecules only. In spin coating, even if the already deposited polymer is not soluble in the solvent used to deposit the overlaid layer, even a small amount of swelling will ensure interpenetration of the two layers and one may then expect that polymer polymer interfaces will in fact be thin mixed layers. Which microscopic structure is at present unknown and recombination will take place within such layers. Indeed, pulsed injection experiments have shown striking differences between the transient behaviors of small molecules and polymer bilayer diodes.
35

CHAPTER III. SAMPLE PREPARATIONS AND EXPERIMENT 3.1. SAMPLE PREPARATION
For preparing OLEDs the following layers have been made: By electron beam deposition: transparent electrically conducting ITO films used as anode Spin coating: PVK used as HTL and MEH-PPV used as emitting layer; Vacuum evaporation: Alq3 used as emitter and Al or Ag used as cathode
3.1.1. Transparent anode (ITO)

Indium tin oxide (ITO) is a degenerate n type semiconductor with a wide band gap and consequently has high electrical conductivity and transmits the visible light. Various deposition techniques such as sputtering, spray pyrolysis, sol gel processes and electron beam evaporation have been used to produce ITO films. The electron beam evaporation technique is a promising method for producing ITO films with lower resistively and higher transmittance. Thermal evaporation (TE) using resistive boats like W, Mo, Ta, etc. is a simple technique but it has also some limitation in evaporation of materials with a high temperature of vapor phase. There are some advantages in electron beam technique in the experiments and studies: We have a pure ambiance for depositing due to a high vacuum We need no resistive evaporation boat which is often chemically active with an initial material, especially at a high temperature It is easy to prepare a crucible with the initial material of a small mass We can control the evaporation, thus creating the appropriate conditions for depositing the films By using multiple crucibles, some different films can be deposited successively Fig. 11 showed the scheme of vacuum equipment combining an electron gun where 36

electron beam are created from a tungsten filament and focused onto the crucibles by controlling the electric parallel magnets. The deposition power can be reached by adjusting the high voltage (U) up to 10 kV and the cathode current heating the filament.
Fig.11. The scheme of vacuum equipment combining an electron gun
3.1.2. PVK and MEH-PPV

The PVK and MEH-PPV powders were prepared in solution with pure cloruaform and xylene, respectively. The solutions were put onto glass or ITO substrates, and then attached to a surface of the spin-coating set-up. The experimental conditions of the spin and heating were chosen to get uniform films with a thickness ranging from 100 nm to 200 nm
3.1.3. Alq3 and Al/Ag films

LiF, Alq3 amd Al or Ag coatings were successively evaporated in a VHD3D unit with a vacuum as high as 10-5 Torr. Resistance boats of Ta and W were used, respectively for LiF, Alq3 and metallic Al/Ag. The thickness of the LiF layer 37

was as low as 10 to 30 nm. The other evaporated films have been much thicker, for instance, the thickness of Alq3 layer is about 100 nm, Al/Ag is about 200 nm.
3.2. CHARACTERIZATION METHODS 3.2.1. Raman spectrometer

Raman spectroscopy (RS) gives relevant information about the mechanisms in polymers. Concerning RS, one showed the mathematical decomposition of spectra and allowed a semiquantitative description of the films. Micro Raman spectra were recorded by using a multichannel Raman spectrometer (RAMLAB 1B), with 632,5 nm Hellion laser line, a 11 mW power at the laser output (the power is about a tenth of this value on the sample surface owing to the microscope optical elements) and an integration time of 1 or 2s. Under these conditions, the stability the films under the light was checked previously. The time necessary for a spectral acquisition was generally 3 min 20s, a wave number range extending 700 cm-1 was investigated at each scan. In stretching mode extends between 1100 and 3000 cm-1. The wave numbers can be considered as given with a precision not better than ca. 2 cm-1. The mathematical decomposition of spectra is made using Spectra Calc software. A standardization of spectra was shown to give relevant results.
3.2.2. Cyclic voltametry

Cyclic voltametry determine the electrochemical current voltage (IV) characteristics of an electrochromic electrode and device. Here we used PU H1 potentiostat in conjunction with a PU H1 universal programmer. A standard three electrode configuration including working electrode (ITO, Fe), reference electrode (SSE, SCE) and counter electrode (Pt grill) were used. A typical voltametry is diagrammed in Fig. 12 , I V characteristic curves to analyze the electrochemical properties of the deposited films. According to the shape of these curves as well as oxidation and reduction peaks, we can describe the mechanisms of polymerizing processes.
38
Fig. 12 Experimental set up for I V measurement
3.2.3. Scanning electron microscopy

Because seeing is reliable and understanding, the SEM is perhaps the most widely employed thin film and coating characterization instrument. A schematic of the typical SEM is shown in Fig. 13. Electrons thermionically emitted from a tungsten or LaB6 cathode filament are drawn to an anode, focused by two successive condenser lenses into a beam with a very fine spot size (~ 50 A0). Pairs of scanning coils located at the objective lens deflect the beam either linearly or in rater fashion over a rectangular area of the specimen surface. Electron beams having energies ranging from a few thousand to 50 keV, with 50 keV a common value, are utilized. Upon impinging on the specimen, the primary electrons decelerate and in losing energy transfer it inelastically to other atomic electrons and to the lattice. Through continuous random scattering events, the primary beam effectively spreads and fills a teardrop shaped interaction volume with a multitude of electronic excitons. The result is a distribution of electrons that manage to leave the specimen. In addition, target X rays are emitted and other signals such as light, heat and specimen current are produced and the sources of their origin can be imaged with appropriate detector. 39
Fig. 13. Scheme of the scanning electron microscope
40

CHAPTER IV. RESULTS AND DISCUSSION 4.1. OLED WITH STRUCTURE OF ITO/MEH PPV/Ag
In this structure, ITO is used as an anode. An active layer, a prospective emitter is poly(2-methoxy,5-(2'-ethylhexyloxy)-1,4-phenylene vinylene), so-called MEH-PPV. The PPV polymer emits blue light (with wavelength of ca. 480 nm), whereas MEH-PPV can emit light from blue to green color, depending on the conjugation ratio between MEH and PPV compounds; and the last, a metallic layer, Ag vacuum-evaporated coating (50 nm thickness) is served as cathode. Transparent electrically conducting films ITO were deposited by electron beam technique. To enhance workfunction of the ITO films, thermal annealing was used. Chemical synthesis of MEH-PPV followed a similar procedure as described by Wudl and the MEH- PPV precursor was synthesized by the conventional Wessling method.
4.2. OLED WITH STRUCTURE OF ITO/PVK/MEH-PPV/Ag

It has been known that efficient OLED device operation requires optimization of three factors: (i) equalization of injection rates of positive (hole) and negative (electron) charge carriers (ii) recombination of the charge carriers to form singlet exciton and (iii) radiative decay of the excitons. In the structure with two carriers, electrons have the lower mobility and hence limit the current conduction process. By adding a hole transport layer (HTL) PVK to the three-layer device ITO/MEH-PPV/Ag one can expect the equalization of injection rates of hole and electron, consequently to obtain a higher electroluminescent efficiency of the OLED. Poly(N-vinylcarbazole) (PVK) is not only a photoconductive polymer but also a photoluminescent one. These properties are well known for a long time but since electroluminescent devices and organic light emitting diodes (OLED) have been achieved, the PVK thin films are under studies. PVK has some advantages, for instance, transmittance in visible range is high, the work function is matched to ITO and PVK film is easy deposited by vacuum evaporation using tantalum resistance 41

boats. Moreover, PVK itself is a photoluminescent (PL) material, the PL emission from PVK film extends from 350 to 600 nm with a maximum at 404 nm and a shorter wavelength shoulder at 385 nm. However, using single PVK as an emitter material is not very efficient because the PL intensity is low and the onset electric field is rather high. So, we have a diode of the structure like ITO/PVK/MEHPPV/Ag. Preparation of ITO/MEH PPV/Ag has been presented above. MEH-PPV films onto ITO and PVK were casted in nitrogen with thickness of ca. 1 m and active area of 0.1 cm2. Raman scattering measurements were carried out on a Dilor Jobin-Yvon Spex LAMBRAM -1B Raman scattering spectrometer. IV characteristics were measured using an Autolab. Potentiostat PGS-30. The thickness of ITO films was measured on the cross-sectional micrographs made by using a LEICA STEREOSCAN 440 electron scanning microscopy to reveal. Resistivity () of the films was then determined through the experimental data of the sheet resistance (R ) and measured thickness (d).
4.2.1. Hole transport layer (HTL) PVK

Fig.14 shows the Raman spectra the PVK thin film. This spectrum is completely consistent with that of the standard PVK. Many previous works, for instance [10], have been shown that to improve the stability and efficiency of OLEDs it is important to decrease the operating bias voltages, i.e. fields, so that the power consumption and hence the Joule heating of the devices is reduced. A reduction of operating fields is crucial not only to reduce temperature effects in the polymer but also to decrease field quenching effects of the excited species. By introducing PVK layer between the anode (ITO) and the polymer (MEH-PPV) one can reduce the barrier height, because with such a high hole mobility of PVK, the HOMO level of the HTL is located above the valence band of the polymer and below the Fermi level of the ITO.
42
500
400
1): PVK powder 2): PVK/ITO thin film
Intensity (a.u.)
300
200
100
2
0 0 300 600 900 1200
-1
1500
1800
Wavenumber (cm )
Fig.14. Raman spectra of PVK thin film
4.2.2. MEH PPV emitting layer

Thick films of MEH-PPV were deposited onto PVK/ITO by using a casting technique in dry nitrogen with low pressure for 8 hours. The Raman spectra of the MEH-PPV film is completely consistent with that of the initial powder and the characteristic bands of the film were found at wavenumbers of 599, 965, 1113, 1283, 1310, 1582 and 1624 cm-1 in Fig.15 for all the samples. Among Raman bands (963, 1170, 1326, 1414, 1546, 1583 and 1624 cm-1) of PPV two bands at 1326 and 1624 cm-1 characterize vibration of vinylene group, the bands at 1170, 1546 and 1583 cm-1 - aromatic cycles. The PPV is a polymer combining intermediate 43

structure between polyacetylene and polyphenylene, it can be seen as a copolymer of acetylene and benzene. Comparing the Raman spectra of MEH-PPV to that of PPV one can see that aromatic cycles in the MEH-PPV have been strongly changed. This enables the polymer to emit light other than that from PPV.
1400 1200 1000

Intensity (a.u)
'1' - MEH-PPV film '2' - MEH-PPV powder
800
1
600 400 200
2
0 400 800 1200
Wavenumber (cm )
-1
1600
2000
Fig. 15 The Raman spectra of MEH PPV thin film
4.2.3. Electrical property (I - V characteristic)

The influence of charge transport PVK layer in MEH-PPV devices can be well described by looking at the properties and performance of a three-layer and four-layer electroluminescent devices using MEH-PPV as emitter, ITO as anode and Ag as cathode. In Fig. 16 there are present plots of the Current-Voltage (IV) characteristics of a three- layers and a four-layers OLEDs. By applying a PVK as 44

HTL between ITO and MEH-PPV, the electric field required for the onset of the current in the forward direction is decreased. For ITO/PVK/MEH-PPV/Ag structures the onset of the electric field occurs at values of around 10 MV/m compared to 15 MV/m obtained for ITO/MEH-PPV/Ag devices. These electrical field values are corresponding to bias voltages of 12.5 V and 17.2 V, respectively for the four-layers and the three-layers OLEDs. The decrease of the onset electric field with application of PVK as the HTL can be attributed to a reduction of the barrier height at the anode/HTL interface.
1.6
1.2
: ITO/PVK/MEH-PPV/Ag : ITO/MEH-PPV/Ag
Current (mA/cm )
0.8
0.4
0.0
-0.4 -20 -10 0 10 20 30 40

Electric field (MV/m)
Fig. 16 The I-V characteristic of ITO/PVK/MEH-PPV/Ag and ITO/MEH-PPV/Ag
45

4.2.4. Discusion
OLEDs have been prepared from multiple layers: the ITO as anode was made by electron beam deposition followed by post-annealing, PVK as HTL was spin-coated, MEH-PPV as an emitter was casted in dry introgen and silver thin film as cathode was vacuum evaporated. ITO, deposited on glass substrates have been treated by thermal annealing in order to improve their quality for use in the OLEDs. Both the PVK and the MEH-PPV films obtained have the same Raman characteristic bands of the initial powder. The current-voltage measurements of the OLEDs showed the significant decrease of the onset electric field due to the reduction of the barrier height at the anode/HTL interface of the OLEDs with application of PVK.
4.3. OLED WITH STRUCTURE OF ITO/PVK/Alq3/LiF/Al

In OLED, both operating voltage and luminance efficiency of the devices strongly depends on effective charge injection from the electrodes to the organic medium and charge transport in the organic materials. In general, to achieve the lowest possible voltage it is necessary to have Ohmic interfaces between the organic layers and the charge-injecting contacts and to maximize the drift mobility of both types of carriers. In this structure, Alq3 is used as both HTL and ELT. Tris (8 hydroxyquinolinato) aluminum (Alq3) was used as an emissive material, which emits in the green with a broad emission peaking at 530 nm. PVK played a role of a hole transport material. An onset voltage was obtained as low as 6.8 V for these devices and no reverse current was observed. The enhancemet in both the onset electric field and the reverse current was explained due to lowering the workfunction of Al/Alq3 by the application Alq3 material. So it can have higher possibility of emissive recombination of excitons in the devices. In this multiply layers diode ITO is used as a transparent anode, HTL Hole transport layer PVK , ELT Electron transport layer, it is LiF and Al melt is used as cathode. Indium tin oxide (ITO) is a degenerate n type semiconductor with a wide band gap and consequently has high electrical conductivity and transmits the visible 46

light. Various deposition techniques such as sputtering, spray pyrolysis, sol gel processes and electron beam evaporation have been used to produce ITO films. The electron beam evaporation technique is a promising method for producing ITO films with lower resistivity and higher transmittance. In the In2O3 crystalline structure, the replacement of In3+ by Sn4+ affects the optical and electrical properties of the ITO films. The replacement produces free electrons that contribute to enhancing the conductivity. All the films such as PVK, Alq3, and LiF have been prepared by vacuum evaporation, using Ta resistance boats. Initial materials for evaporation were of PVK, Alq3 and LiF crystalline powders which were purchased from Aldrich Ltd. Chemical pure produces. 5N-pure aluminum wire has been used for evaporation from W-basket boats. Aluminum coatings used as cathode with thickness of 100 nm were evaporated onto the polymer and composite films. The measurement some multiple-layer devices of ITO/PVK/Alq3/LiF/Al were annealed at 200 0C in vacuum of 2 x 10-2 Torr for 2 hours.
4.3.1. I-V characteristic of the device

The super thin layer (the thickness ranged from 0.1 to 1.0 nm) LiF has formed a shallow contact Al/LiFAlq3 instead of AlAlq3. This contact improves the electron transport from the high workfunction cathode into the emissive layer. Fig. 17a presents a typical IV-curve of the multiple-layer organic light emitting diode with ITO/PVK/Alq3/ LiF/Al structure. From this figure one can note that: The onset voltage of the device is rather low, it consists of only 6.8 V which is much smaller than that of ITO/PVK/MEH-PPV/Ag The reverse current a factor causes non-emitting recombination of the excitons generated in the emissive layer is almost eliminated. These results strongly demonstrate the important role of the HTL and ETL in OLEDs. Indeed, the photoluminescence (PL) curve of the diodes exhibited these advantages in the current density of lighting Fig. 17b. It is seen from this figure that 47

although the diode emitted with a small current density, namely 6 nA/cm2, the PL curve has such a high abrupt increase in the intensity that, if it is possible to maintain, one can expect a good lighting from the OLED. The fact that the PL is unstable can probably be explained due to a bad contact of the metallic wire with ITO-anode and/or Al-cathode. This is just needed to carry-out further investigation of both the preparation techniques and capsulation in a much cleaner room.
3.5
6
3.0
EL, nA/cm2
5
Current density (/cm2)
Current density (nA/cm2)

-1 0 1 2 3 4 5 6 7 8
2.5 2.0 1.5 1.0 0.5 0.0
0
-0.5
-2
-4
-6
-8
Voltage (V)
Voltage (V)
a).
b).
Fig. 17. IV (a) and PL (b) characteristics of a multiple-layer OLED with

ITO/PVK/Alq3/ LiF/Al structure
4.3.2. Discussion
Multiple-layer-structured OLEDs based on tris(8-hydroxyquinolinato) aluminum (Alq3) were prepared for researching the role of both the hole and electron transport layers in electrical and electroluminescent properties. An onset voltage (Vons) was obtained as low as 6.8 V for these devices, and no reverse current was observed. The enhancement in both the onset electric field (onset voltage) and the reverse current has been obtained. This is explained due to the better injection of electrons from the Al-cathode into the emissive Alq3 material. For these devices a PL-current density of 6 nA/cm2 has been reached.
48

4.4. PHOTOLUMINENSCENT OF NANOSTRUCTURED PVK + TiO2 COMPOSITE PVK/nanoparticle TiO2 (PVK+ nc-TiO2) composite film has proved the advantage in the optical and electrical properties of the composite structure in comparison with those of the homogeneous polymers. Transparent electrically conducting films (ITO) were deposited by electron beam technique that can be seen elsewhere [3]. To enhance workfunction of the ITO films, thermal and chemical treatments have been used [4]. To prepare PVK + nc-TiO2 composite films, a mixture of TiO2 anatase nanocrystalline powder with the 70 nm size particles (received from the Degussa comercial products) and PVK crystalline powder has been prepared. Mixture with a TiO2/PVK weight ratio (WR) ranging from 0.25 to 0.75 was dissolved in monochrolobenzene by ultrasonic shaking. Both the PVK and PVK + nc-TiO2 composite films were prepared by spin coating method, using two these solutions. Aluminum coatings used as cathode with thickness of 100 nm were evaporated onto the polymer and composite films. The measurement ITO/PVK+nc-TiO2/ Al was annealed at 200 0C in vacuum of 2 x 10-2 Torr for 2 hours.
4.4.1. Raman spectra

Fig. 18 shows the Raman spectra the PVK thin film onto ITO (PVK/ITO). This spectrum is completely consistent with that of the PVK powders. Many previous works, for instance [5], have been shown that to improve the stability and efficiency of OLEDs it is important to decrease the operating bias voltages, i.e. fields, so that the power consumption and hence the Joule heating of the devices is reduced. A reduction of operating fields is crucial not only to reduce temperature effects in the polymer but also to decrease field-quenching effects of the excited species. By introducing PVK layer between the anode (ITO) and the polymer (MEH-PPV) one can reduce the barrier height, because with such a high hole mobility of PVK, the HOMO level of the HTL is located above the valence band of 49

the polymer and below the Fermi level of the ITO. The fact that Raman spectra of the PVK+ nc-TiO composite do not show any different bands than those of the standard PVK proves that the composite made by the spin-coating technique is formed as a simple mixture where the inorganic particles were surrounded by polymer.
500
A ) - P V K film B ) - C o m p o s ite film

400
Intensity (a.u.)
300
200
100
B
0 300 600 900 1200
-1
1500
)
W a v e n u m b e r (c m
Fig.18 Raman spectra of a homogenous PVK (A) and a nanocomposite (with WR=0.35)
spin-coated film (B)
4.4.2. Photoluminescent property

It is known that PVK has an absorption maximum at about 350 nm consisting with the absorption range of glass, the absorption of both the standard polymer and composite films could not revealed, while the PVK and the composite were deposited onto ITO coated glass. However, studying the photoluminescent (PL) property of the films enables us to be aware of useful information about the 50

polymer and the composite. An interesting result of this study is present in Fig. 19 where there is observed a considerably large difference in the PL intensity between homogenous PVK and the PVK+ nc-TiO2 composite. From this figure one can note that this difference appears in two characteristics: (i) the blue shift of PL maximum and (ii) the PL intensity increase. The first difference indicates that the TiO2 particles in the interlayer are quantum size. To explain the second difference we consider the PVK/nc-TiO2 composite as a system consisting of oxideparticles/polymer transition boundaries
4 0 0 0
2
3 0 0 0
Intensity
1 ) - P V K 2 ) - c o m p o s ite
2 0 0 0
1 0 0 0
4 0 0
5 0 0
6 0 0
7 0 0
8 0 0
9 0 0
W a v e le n g th
Fig. 19 Photoluminescent spectra of homogenous PVK (1) and nanocomposite

(WR=0.35) spin-coated film (2)
4.4.3. I-V characteristics

The role of the nanocomposite emitting material in the electroluminescent devices can be seen by comparing of I V characteristics of the devices made from the standard homogenous PVK and PVK + nc-TiO2 composite. These devices have structure like ITO/PVK/Al and ITO/PVK+nc-TiO2/Al, respectively called ELD and CELD. Fig. 5 shows the plots of IV characteristics of the devices. It seems that 51

electrical behavior of the CELD exhibit a contrary way to the PL effect. For the CELDs the electric field required for the onset of the current in the forward direction is increased: the turn-on voltage occurs at values of around 5 V, while it is of 3 V obtained for the ELDs.
0 .0 2 5 0 .0 2 0 0 .0 1 5 0 .0 1 0
1 )- P V K 2 ) - P V K + T iO
Current (A)
1
0 .0 0 5 0 .0 0 0 0 2 4 6 8 1 0
V o lta g e (V )
Fig. 20 IV-characteristics of ITO/PVK/Al (ELD) (1) and ITO/PVK+nc-TiO2/Al (CELD)

(2) diodes.
However, Fig. 20 also shows a prospective feature in the IV chracteristic of the composite. In the CELD the reverse current intensity is maintained at zero till the turn-on voltage of the device appears, whereas in the ELDs this current starts increasing from the beginning. It is known that the reverse current increase strongly affect the diode performance. Both the increase of the onset electric field (or turn-on voltage) and the decrease of the reverse current with application of nanocomposite proves the formation of the Shottky barrier at the oxide particles/polymer interface in the polymer/oxide composite. 52
4.4.4. Discussion
Organic Light-Emitting Diodes (OLEDs) using PVK and PVK/TiO2 nanocomposite have been prepared from multiple layers: the ITO as anode was made by electron beam deposition followed by post-annealing, PVK and PVK + ncTiO2 films as emitter were spin-coated and aluminum thin film as cathode was vacuum evaporated. SEM and Raman scattering spectra characterization of the PVK and PVK/nc-TiO2 films have shown that the nanocomposite was formed as a polymeric matrix where the inorganic particles were surrounded by polymer. The photoluminescent and current-voltage characteristics measurements of the OLEDs have demonstrated both the improvement in PL intensity and the significant decrease of the reverse current. These enhancements were explained due to the reduction of the Shottky barrier height at the nanoparticles/polymer interface of the OLEDs with application of nanocomposite.
53

CONCLUSION
This work was done some polymers and conjugate polymers used for organic light-emitting diodes (OLEDs), from the study the following conclusions were obtained: Main optical and electroluminescent properties of polymers have been elaborated from references; Two types of organic light-emitting diodes have been prepared for study, they are ITO/PVK/MEH-PPV and ITO/PVK/Alq3/LiF/Al where ITO used as anode has been produced by electron beam deposition; Al, Ag, Alq3 by spin coating. By addition of PVK layer as hole transport layers between the ITO and MEH-PPV, both the I-V and photoluminescent (PL) characteristics of ITO/PVK/MEH-PPV/ Ag devices have been enhanced. For organic light-emitting diodes (OLEDs) with both hole transport layer (HTL) and electron transport layer (ETL) like ITO/PVK/Alq3/LiF/Al the onset voltage is much lower than the one of the structure with only hole transport layer (HTL) like ITO/PVK/MEH-PPV/Ag. This effect is explained due to increase of emitting recombination possibility of excitons generated in the emissive layer. A nanostructured composite film of PVK+nc- TiO2 has been prepared by spin-coating. The result showed that the nanocomposite was formed as a polymeric matrix where the inorganic particles were surrounded by polymer. Photoluminescent intensity (PL) of the composite has been much stronger (namely one order in magnitude) in comparison with a standard PVK film.
54

REFERENCES
1. A.J.,Chem.Commun., 1977:578 2. Nigrey, P.J., MacDiarmid, A.G. and Heeger, A.J.,Chem. Commun.,1988, 60:781 3. Heeger, A.J., Kivelson, S.,Schrieffer, J.R. and Su, W.P., Rev. Mod. Phys.,1988,60:781 4. E.Gurnee, R.Ferander, US Patent (1965) 5. Rhoderick E.H.,Williams R.H., Metal-Semiconductor Contacts, Oxford University Press, 1988 6. Horowitz,G., Organic field-effective transitors, Adv.Mater.10 (1998) 7. N. N. Dinh, T. Q. Trung, L. H. Mai, P.D. Long, T. P. Nguyen, Communications in Physics, 13 (2003) No.3, p. 165
55

CONTENT
Page ABTRACT...................................................................................................................1 INTRODUCTION ......................................................................................................4 CHAPTER I. OVERVIEW OF CONDUCTING POLYMERS ...............................5 1.1.THE BASIC CONCEPT ...................................................................................5 1.2. THE CLASSIFICATION ................................................................................6 1.2.1. Chemical doping by charge transfer .....................................................6 1.2.2. Electrochemical doping ..........................................................................7 1.2.3. Doping of polyaniline by acid-base chemistry......................................8 1.2.4. Photo-doping............................................................................................9 CHAPTER II. ORGANIC LIGHT-EMITTING DIODE (OLED) ........................11 2.1. INTRODUCTION..........................................................................................11 2.2. DEVICE CONFIGURATION .......................................................................12 2.3. THE OPERATION ........................................................................................14 2.3.1. Injection .................................................................................................16 2.3.2. Carrier transport ..................................................................................16 2.3.4. Carrier recombination..........................................................................17 2.3.4. Photon emission.....................................................................................18 2.3.5. Photon extraction ..................................................................................19 2.4. THE PARAMETERS.....................................................................................19 2.5. CURRENT LIMITING FACTORS...............................................................20 2.5.1. Current limiting factors........................................................................20 2.5.2. Unipolar bulk limited (space charge limited) current .................22 2.5.3. Double injection (bipolar) bulk limited current...........................23 2.5.4. Electrode limited currents.................................................................24 2.5.5. Thermionic injection currents in organic materials ..........................24 56

2.6. MATERIALS.................................................................................................26 2.6.1. The organic emitting materials ............................................................26 2.6.2. The materials for cathodes ...................................................................29 a. Mg Ag metallic films .............................................................................29 b. Li Al films ..............................................................................................29 c .LiF/Al films...............................................................................................29 2.6.3. The materials for Anodes .....................................................................30 2.7. DIFFERENT TYPES OF OLED ...................................................................30 2.7.1. The single of OLED...............................................................................30 2.7.2. Multilayer diodes...................................................................................32 CHAPTER III. SAMPLE PREPARATIONS AND EXPERIMENT ...................36 3.1. SAMPLE PREPARATION ...........................................................................36 3.1.1. Transparent anode (ITO) .....................................................................36 3.1.2. PVK and MEH-PPV .............................................................................37 3.1.3. Alq3 and Al/Ag films.............................................................................37 3.2. CHARACTERIZATION METHODS...........................................................38 3.2.1. Raman spectrometer.............................................................................38 3.2.2. Cyclic voltametry ..................................................................................38 3.2.3. Scanning electron microscopy..............................................................39 CHAPTER IV. RESULTS AND DISCUSSION....................................................41 4.1. OLED WITH STRUCTURE OF ITO/MEH PPV/Ag .................................41 4.2. OLED WITH STRUCTURE OF ITO/PVK/MEH-PPV/Ag..........................41 4.2.1. Hole transport layer (HTL) PVK ........................................................42 4.2.2. MEH PPV emitting layer ..................................................................43 4.2.3. Electrical property (I - V characteristic) ............................................44 4.2.4. Discusion ................................................................................................46 4.3. OLED WITH STRUCTURE OF ITO/PVK/Alq3/LiF/Al .............................46 4.3.1. I-V characteristic of the device ............................................................47 57

4.3.2. Discussion...............................................................................................48 4.4.1. Raman spectra.......................................................................................49 4.4.2. Photoluminescent property ..................................................................50 4.4.3. I-V characteristics .................................................................................51 4.4.4. Discussion...............................................................................................53 CONCLUSION.........................................................................................................54 REFERENCES ........................................................................................................55
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Study of optical and electroluminescent properties of conjugated polymers

VIETNAM NATIONAL UNIVERSITY, HANOI COLLEGE OF TECHNOLOGY

STUDY OF OPTICAL AND ELECTROLUMINESCENT PROPERTIES OF CONJUGATED POLYMERS

THESIS FOR THE DEGREE OF BACHELOR OF SCIENCE IN TELECOMMUNICATIONS

Assoc.Prof.Dr. Nguyen Nang Dinh

Study of optical and electroluminescent properties of conjugated polymers

Study of optical and electroluminescent properties of conjugated polymers

Study of optical and electroluminescent properties of conjugated polymers

Study of optical and electroluminescent properties of conjugated polymers

Study of optical and electroluminescent properties of conjugated polymers

1.2.1. Chemical doping by charge transfer

( polymer)n + [Na+ (Napthtalide) ]y [(Na+ )y ( polymer) y ]n + (Naphth)o

Study of optical and electroluminescent properties of conjugated polymers

Fig.1. Doping mechanisms and related applications

Study of optical and electroluminescent properties of conjugated polymers

( polymer )n + [Li + (BF4 )]sol 'n [( polymer )(BF4 )y ] n + Li(electrode)

( polymer )n + Li (electrode) [(Li + )y ( polymer ) y ]n + [Li + (BF 4 )]sol 'n

Study of optical and electroluminescent properties of conjugated polymers

Fig.2. Protonation induced spin unpairing in polyanline; conversion from insulator to

( polymer )n + h [{ polymer}+ y + { polymer} y ]n

Study of optical and electroluminescent properties of conjugated polymers

Study of optical and electroluminescent properties of conjugated polymers

CHAPTER II. ORGANIC LIGHT-EMITTING DIODE (OLED) 2.1. INTRODUCTION

Study of optical and electroluminescent properties of conjugated polymers

2.2. DEVICE CONFIGURATION

Study of optical and electroluminescent properties of conjugated polymers

Fig.4. Energy level diagram of a two layer OLED

Study of optical and electroluminescent properties of conjugated polymers

2.3. THE OPERATION

Study of optical and electroluminescent properties of conjugated polymers

Study of optical and electroluminescent properties of conjugated polymers

2.3.2. Carrier transport

Study of optical and electroluminescent properties of conjugated polymers

2.3.4. Carrier recombination

Study of optical and electroluminescent properties of conjugated polymers

2.3.4. Photon emission

Study of optical and electroluminescent properties of conjugated polymers

2.3.5. Photon extraction

2.4. THE PARAMETERS

Study of optical and electroluminescent properties of conjugated polymers

2.5. CURRENT LIMITING FACTORS 2.5.1. Current limiting factors

Study of optical and electroluminescent properties of conjugated polymers

Study of optical and electroluminescent properties of conjugated polymers

To be compared to the transit time t ( ) :

Study of optical and electroluminescent properties of conjugated polymers

2.5.3. Double injection (bipolar) bulk limited current

Study of optical and electroluminescent properties of conjugated polymers

And the ratio of recombination time to transit time becomes:

2.5.5. Thermionic injection currents in organic materials

Study of optical and electroluminescent properties of conjugated polymers

- the Schottky effect leading to a current

Study of optical and electroluminescent properties of conjugated polymers

2.6.1. The organic emitting materials

Study of optical and electroluminescent properties of conjugated polymers

Study of optical and electroluminescent properties of conjugated polymers

Study of optical and electroluminescent properties of conjugated polymers

2.6.2. The materials for cathodes

Study of optical and electroluminescent properties of conjugated polymers

2.6.3. The materials for Anodes

2.7. DIFFERENT TYPES OF OLED 2.7.1. The single of OLED

Fig.7. Structure of single OLED

Study of optical and electroluminescent properties of conjugated polymers

Study of optical and electroluminescent properties of conjugated polymers