7065455هااااام | Oled | Doping (Semiconductor)

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

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Study of optical and electroluminescent properties of conjugated polymers
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

Study of optical and electroluminescent properties of conjugated polymers
composite was quite different than for a standard PVK film: the photoluminescent intensity of the nanocomposite was increased nearby one order in magnitude.

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Study of optical and electroluminescent properties of conjugated polymers
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

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Study of optical and electroluminescent properties of conjugated polymers
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 π-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 π-bonded

Concurrent with the doping.2. Chemical doping by charge transfer The initial discovery of the ability to dope conjugated polymers involved charge transfer redox chemistry. Charge injection onto conjugated. leads to the wide variety of interesting and important phenomena which define the fields. many different kinds of conducting polymer were made. one should depend on their structure and mechanism doping. as illustrated with the following examples: p-type: (π − polymer ) n-type: n + 3 / 2ny ( I 2 ) ⎯ (π − polymer ) ⎯→ [ +Y (I ) ] − 3 y n (1) (π − polymer)n + [Na+ (Napthtalide)• ]y ⎯ [(Na+ )y (π − polymer)− y ]n + (Naphth)o ⎯→ metal. “doping”. therefore. can be accomplished either by chemical doping or by electrochemical doping.2. THE CLASSIFICATION Today.1. the electronic structure evolves to that of 6 . The electrical conductivity results from the existence of charge carriers (through doping) and from the ability of those charge carriers move along the π .bonded “highway”. charge neutrality is maintained by the introduction of counter – ions. Reversible charge injection by “doping” can be accomplished in a number of ways: 1. salts.Study of optical and electroluminescent properties of conjugated polymers 1. semiconducting macromolecular chains. Metallic polymers are. (2) When the doping level is sufficiently high. To classify. 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. with associated control of the electrical conductivity over the full range from insulator to metal. oxidation (p-type doping) or reduction (n-type doping) [1]. Reversible “doping” of conducting polymers.

2.1. while ions diffuse into (or out of) the polymer structure from the nearby electrolyte to compensate the electronic charge.2. In electrochemical doping.electrode. at electrochemical equilibrium the doping level is precisely defined by that voltage. the electrode supplies the redox charge to the conducting polymer. Electrochemical doping was invented to solve this problem [2].Study of optical and electroluminescent properties of conjugated polymers Fig. Doping mechanisms and related applications 1. doping at 7 . 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 Although chemical (charge transfer) doping in an efficient and straightforward process. The doping level is determined by the voltage between the conducting polymer and the counter . Thus. it is typically difficult to control.

base chemistry leads to an internal redox reaction and the conversion form semiconductor (the emeraldine base) to metal (the emeraldine salt). Electrochemical doping is illustrated by the following examples: p-type: (π − polymer )n + [Li + (BF4 − )]sol 'n ⎯ [(π − polymer )(BF4 − )y ] n + Li(electrode) ⎯→ n-type: (3) (π − polymer )n + Li (electrode) ⎯ [(Li + )y (π − polymer )− y ]n + [Li + (BF − 4 )]sol 'n ⎯→ 1.2. HSO4 − .2. DBSA− etc. Cl − . a metallic state where there is a positive charge in each repeat unit (from protonation) and an associated counter – ion (e. This remarkable conversion from semiconductor to metal has been well described. the counter – ion is not shown in Fig. The chemical structure of the semiconducting emeraldine base form of polyaniline is that of an alternating copolymer. potentially. 8 . Protonation by acid . 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. 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. Doping of polyaniline by acid-base chemistry (4) Polyaniline provides the prototypical example of a chemically distinct doping mechanism.2).g. The result is a half-filled band and. The doping mechanism is schematically in Fig.2. Upon protonation of the emeraldine base to eth emeraldine salt.Study of optical and electroluminescent properties of conjugated polymers any level can be achieved by setting to come to electrochemical equilibrium (as indicated by the current through the cell going to zero).3. but it is not well understood from the view of basic theory.

conversion from insulator to metal with no change in the number of electrons 1.4.2. 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. Protonation induced spin unpairing in polyanline. 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): (π − polymer )n + hν ⎯ [{π − polymer}+ y + {π − polymer}− y ]n ⎯→ (5) Where y is the number of electron – hole pairs (dependent upon the pump rate in competition with the recombination rate).Study of optical and electroluminescent properties of conjugated polymers Fig. 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 .2.

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

Organic electroluminescence (EL) is the electrically driven emission of light form non-crystalline organic materials.3. Great strides have been made towards the development and improvement of molecular materials for display applications. research activities in this new field and enormous progress has been made in the improvements of color gamut. The most critical performance characteristic for OLEDs is the device operational lifetime. which combined modern thin film deposition techniques with suitable materials and structure to give moderately low bias voltages and attractive luminance efficiency. As a consequence. Continuous operation of OLDEs generally leads to a steady loss of efficiency and a gradual rise in bias voltage. various OLED displays have been demonstrated. the material issues underlying the EL degradation are not fully understood. luminance efficiency and device reliability. The growing interest is largely motivated by the promise of the use of this technology in flat panel displays. Although OLEDs have achieved long operational stability. ORGANIC LIGHT-EMITTING DIODE (OLED) 2. INTRODUCTION Electroluminescence is the light emitted by a solid through which an electric current is passing. a team in Kodak introduced a double layer organic light-emitting device (OLED). Molecular structures of a few conjugated polymers CHAPTER II. in addition to its normal thermal emission. which was first observed and extensively studied in the 1960s [4]. Since then.Study of optical and electroluminescent properties of conjugated polymers Fig. there have been creasing interests. In 1987. It implies the presence of electronic excited states with populations larger than their thermal equilibrium value. The design of EL materials for used in OLEDs is critical to device performance. The promise of low-power consumption and excellent emissive quality 11 . The remarkable advance in OLEDs has led to its application to flat panel displays.1.

injection of holes occurs from the anode into the hole-transport layer (HTL). and the electron current is strongly influenced by the presence of traps owing to metal-organic interactions.2. energy is released as light. 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 interface between the two layers provides an efficient site for the recombination of the injected hole-electron pair and resultant electroluminescence. Current 12 . one organic layer is specifically chosen to transport holes and the other organic layer is specifically chosen to transport electrons. The efficiency of an OLED is determined by charge balance. In a basic twolayer OLED structure. and light extraction. Upon recombination. Light extraction is determined by the device structure and the refractive indices of the composed layers. radiative decay of excitons. In OLEDs. 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. the hole current is limited by injection. and active-matrix full-color displays have been demonstrated.Study of optical and electroluminescent properties of conjugated polymers with a wide viewing angle is unique among display technologies. Significant progress has been made recently in developing phosphorescent emitters via triplet-triplet energy transfer. At the moment. DEVICE CONFIGURATION An OLED has an organic EL medium consisting of extremely thin layers (<0.2 µm in combined thickness) sandwiched by two electrodes. 2. and high-efficiency OLEDs in various colors have been demonstrated. passive monochrome and multicolor displays are commercially available. Charge injection and transport are the limiting factors in determining operating voltage and luminance efficiency. 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. which is emitted from the light-transmissive anode and substrate.

while the lowest unoccupied molecular orbital (LUMO) of the ETL is significantly below that of the HTL.4. 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. while the problem of light-trapping remains unsolved in terms of its application to displays. so that electrons are confined in the ETL. Energy level diagram of a two – layer OLED The low hole mobility in the ETL causes a build up in hole density. Furthermore. Fig. so that holes can readily enter into the ETL. the probability of quenching near the metallic 13 . by spacing this interface at a sufficient distance form the contact. the highest occupied molecular orbital (HOMO) of the HTL is slightly above that of the ETL. and thus enhance the collision capture process.Study of optical and electroluminescent properties of conjugated polymers research activity is directed toward various surface modifications that can increase extraction efficiency. As shown in Fig.4.

In this respect. emission of photon. 2. the function of the individual organic layers is distinct and can therefore be optimized independently. Likewise. 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. the ETL and the HTL can be optimized primarily for the carrier-transport property. The simple structure can be modified to a three-layer structure. as shown on Fig. transport through the structure. the thin layers coupled with increased charge injection and transport efficiencies have allowed acceptable light emission to be achieved at low voltages.Study of optical and electroluminescent properties of conjugated polymers surface is greatly reduced. 14 . Thus. recombination into a neutral excited state.5. THE OPERATION It is convenient to consider the overall operation of an OLED as a sequence of 5 steps: charge injection at the electrodes. Since light emission is directly related to current density through the organic EL medium.3. the luminescent or recombination layer can be chosen to have a desirable EL color as well as high luminance efficiency. transport of the photon out of the diode. The extremely thin organic EL medium offers reduced resistance. permitting higher current densities for a given level of electrical bias voltage.

Schematic drawing of the five elementary steps of EL 15 .5.Study of optical and electroluminescent properties of conjugated polymers Fig.

Study of optical and electroluminescent properties of conjugated polymers 2.1.2. and large efficiencies. accumulation of a large majority carrier density at the minority carrier injection electrode leads to a large potential difference buildup.3. If the recombination efficiency is not large. which complicates a thorough treatment of organic EL. so that most of the majority carriers cannot recombine. Carrier transport Once an electron and a hole have been injected. their extraction may limit the current. and shallow donors or acceptors are absent. Generally. a smaller current imbalance. Such processes may explain the successful operation of ‘symmetrical’ ITO/Anthracene/ITO diodes or the possibility of using ITO as a cathode. This is the first example of the interrelation of different elementary processes. this is the basis of ‘current multiplication’ that has been observed in some organic photo conducting films. Injection The equilibrium concentrations of carriers in the organic materials used are very small: the forbidden gap is large. However. despite the unfavorable positions of energy levels at equilibrium. for instance if the electron and hole densities are very different. electrons may be field injected from ITO. which is not favorable for fast extraction. 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. thus leading to poor diode performance. hole conducting levels of most OLED materials fall in its forbidden gap. 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.3. In fact. 2. injection and extraction are not unrelated. since ITO is a wide gap semiconductor. Therefore. If a large enough ensues. Indeed. hence a large minority current increase. Injection may either proceed over the interface barrier by tunneling [5]. The carriers present in the operating OLED must be injected from the electrodes. they must be transported 16 .

In the organic films used in OLEDs. the socalled bipolarons [6]. because some lattice relaxation around the charge is expected.Study of optical and electroluminescent properties of conjugated polymers through the film to the point where they will recombine. carrier transport is believed to be always by hoping between localized states. chemists would merely speak of radical inons. ‘polaron formation’ then meaning only that the neutral ground state and ion geometries are somewhat different.4. The large recombination efficiency precludes the formation of injected plasma and in fact this is a strong point in favor of OLEDs. This has been well established experimentally in the case of molecular crystals. hence the name of ‘Langevin recombineation’ used for this process. but says nothing about 17 .3. is large. These excited states are usually loosely referred to as polarons. but there is no convincing evidence that they play a role in OLEDs 2. but this does not imply any kind of coherent transport. Carrier recombination The dielectric constant of the organic materials used is always small (typically ε ~ 3-4). typically 15nm at room temperature. The capture then results from a process of diffusion in a field. so Coulomb screening is inefficient and the distance: rc = e2 4πεε 0 kT (6) at which the attractive interaction between an electron and a hole is > kT. The theory describes the carrier approach very well. and this is quite different from the case of semiconductors. as in the case of weakly ionized dense gases treated long ago by Langevin. Hence large capture cross section ( πrc ~ 10-11 cm2) and large recombination rate constants obeying the relation: γr = e(µ + + µ − ) εε 0 (7) independent of any applied field. The formation of doubly charged species in doped conjugated polymers has been assumed.

which depends on the electric field at the exciton position. However.e. 2. The probability of redissociation depends on τe and on the binding energy Eb (the difference between its energy and that of a free electron – hole pair) of the exciton. This has been hotly debated. at high fields. mainly C and H. 10V applied to 100 nm thick film. Implicit in the above is the assumption that it proceeds instantaneously once the carriers are on the same site. The Langevin recombination model does not take electron spin into account. several tenths of an eve. leads to negligible redissociation at room temperature. recombination produces a neutral excited state in the literature as an exciton. but there is up to now no direct proof for this. spin-orbit coupling effects are inefficient. Evidence of this process has been observed in OLED films at high fields ~ 1MV/cm. and neutral excited states are well classified as singlet 18 (S=0) and triplets (S=1). Such a binding energy. However. for singlet exactions . up to 1 eV. the so-called field-assisted dissociation.5 eV for the singlet. It seems now well established that in ‘small molecules’ as well as in conjugated polymers. . i. together with an exciton lifetime ~ 1ns. spin dependent (exchange) interactions would indeed certainly be negligible. Be at zero field is usually quite large for molecular exactions. During the lifetime τe the exciton may be redissociated into a free carrier pair. in an applied electric field E. and in EL field. and this is expected to be a typical value.3. Photon emission Almost all organic materials used in OLEDs are composed of light elements only.7 eV. in PPV. the situation in conjugated polymers has been less clear. the electron spin has consequences on the final neutral excited states produce.and much larger for triplets . Be is accurately known in polydiacetylenes only. at least for conjugated polymers. the barrier is depressed by an amount proportional to exp(βE1/2).Study of optical and electroluminescent properties of conjugated polymers the final recombination step itself. Eb ~ 0.4. Since τe is very large. although a true exciton is a collective excitation of a periodic solid.. This leads to a decrease in recombination efficiency. the generally accepted value is Eb ~ 0. for instance. the most studied EL conjugated polymer emitting in the green. so.

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.3. then the electroluminescence quantum yield is proportion to: η= η s + 3η t 4 (8) 2. so it is smaller than the quantum yield by a factor hν/eV. THE PARAMETERS The internal quantum yield ηiq: is the ratio of the number of generated photons to the number of charges transport through the device. However. and the one for triplet emission.Study of optical and electroluminescent properties of conjugated polymers according to their spins and multiplicity. and the weakness of electron-hole magnetic interaction at large distance. they depend on the operating conditions of the device. The singlet-triplet energy splitting is large (typically 1 eV) The fact that electron and hole have initially no spin correlation. particularly the applied voltage.4. the phosphorescence. the fluorescence. is ηt. 2. The luminous efficiency (lumen per watt) is the photometric equivalent of the external energetic yield weighted by a standard spectral function V(λ) 19 . Photon extraction This last step may have a large influence on the external yields. For display applications this is indeed advantageous. If the quantum yield for singlet emission. is ηs. these yields are not a number characteristic of a device.5. and are smaller by the factor P0. 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. The internal energetic yield ηie (in W/W): is the ratio of energy generated as light (radiant energy) to expended electrical energy. The emitting layer being generally disordered and non textured. higher spin states are generally at too high energies to play any role here. The corresponding external yield ηeq and ηee refer to photons that are emitted in the outer space.

this number is to be multiplied by (ηe + 3 ηt)/4. and its optimization leads to that of other quantities. so the number of recombination events per second is e-1 ηr Jmin . without going into the detailed theory. Finally another photometric quantity of importance is the luminous flux per solid angle unit (the candelea. depending on the understanding and control of the elementary steps of the EL process.Study of optical and electroluminescent properties of conjugated polymers representing the eye response. where ηr is probability of recombination. If this current is large enough another limitation appears. this charge is of the order of that of the corresponding capacitor: 20 . Taken per unit emitting surface. governed by ηee. leading to a space charge limited current. The lumen (lm) is the unit of luminous flux.25 ηs. The recombination of the minority carriers current Jmin. Quantities of practical significance are the luminous efficacy (lm/W) and the luminance L (cd/m2). CURRENT LIMITING FACTORS 2.5. Which one is limiting depends both on the carriers transport properties and on the injection conditions at the electrode. The internal quantum yield is the fundamental quantity of interest for the basic physical description. The internal quantum yield ηiq is then: η iq = (η + 3η t ) J min ηr s J total 4 (9) 2. Consider first the simple case where only one electrode injects carriers.5. then all carriers in the film are of the same sign. one gets the luminance (unit the cd/m2).1. in other words its saturation current. and the current is limited by their space charge. To get the number of emitted photons. or if the singlet exciton is the only radiant state by 0. Qualitatively. the radiant flux weighted by V(λ). The number of charges crossing the film is e-1Jtotal (the total current). that of the total charge present in the bulk of the film. cd = lm/sr). Current limiting factors The current through the diode can be limited by the injecting capability of the electrode.

If the two types of carriers are present. Equivalently. the observed current is smaller and its V and D dependences may be steeper. Jmin must be maximized. if not in transports. recombination is very efficient in organic materials. the actual J is smaller and determined by the electrode (‘injection limited’). under a given applied voltage V. The corresponding ‘bipolar’ current may become larger than predicted by equation (11). To maximize the radiant flux. In the absence of recombination. If the injecting electrode cannot supply that current. so bipolar injection currents are limited by a combination of space charge and recombination. if such conditions are met. so a free-trapped recombination may be almost as efficient as a free-free one. Because trapped charges still take a part in the recombination. If a fraction of the charges is immobilized (trapped). and maximizing ηiq implies a blanced bipolar injection. 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).Study of optical and electroluminescent properties of conjugated polymers Q≈ εε 0 V e D (10) D is the film thickness and ε the dielectric constant of the medium. the corresponding rates are still given by equation (6) with the appropriate µ = 0. their respective space charges compensate at least in part. 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 γ r . If all charges are mobile. However. their motion in the average field V/D generates a current: J ≈ εε 0 µV 2 D3 (11) The exact result differs from (11) by a factor 9/8 only. J may be increase very much. This is largest unipolar current that can flow through the organic film for a given V. a given luminous efficiency will be achieved at the 21 .

That is the highest possible ratio hν/eV. Unipolar bulk – limited (space – charge limited) current An important parameter in determining the EL yield is the probability of recombination of a minority carrier.Study of optical and electroluminescent properties of conjugated polymers smallest possible V. Suppose that the majority carrier (labeled α below) current is space charge limited and that the minority carrier (labeled β below) density is small enough not to significantly perturb these SCL conditions. It may depend on the applied voltage V. the average recombination lifetime of minority carrier τ r (β ) is: τ r (β ) = 1 2 L2 = γ r nα 3(µα + µ β )V (13) To be compared to the transit time τ t (β ) : L2 τ t (β ) = = µ E µ βV L (14) The ratio: 22 . For maximum luminance under a given applied voltage. optimizing the luminous efficiency and luminance. one should then have the largest possible µ. For simplicity.5. So carrier density nα and electric field E by their space averaged values: (a) nα = 3εε 0V . J is proportional to µ. more complicated device structures such as multiplayer diodes must be designed. the injection conditions. we neglect trapping and replace the actual. 2eD 2 (b) E = V D (12) Using the equation (2) for the recombination rate constant of β carrier. transport properties and internal structure of the diode (monolayer or multilayer).2. For a good emitting material with a small µ. 2. position dependent. Under these conditions.

a large µ (β ) means a large value of γ r so recombination remains efficient. In this case. The opposite limit is that of bulk-limited double injection. is: J ≈ εε 0 µ eff V 2 L3 (16) µ eff is in general a complicated function of the µ ’s. • The ratio is independent of D and V. The theory has now been explicitly applied to OLEDs. for 23 . the variation of EL quantum yield with V will reflect the V dependence of the minority carrier injection efficiency. half of the β carriers recombines.Study of optical and electroluminescent properties of conjugated polymers τ (β ) 2 ⎛ µ α r= r = ⎜1 + τ t (β ) 3 ⎜ µ β ⎝ ⎞ ⎟ ⎟ ⎠ −1 (15) gives an idea of the efficiency of the recombination process.5. one finds µ eff ≈ 2. On the other hand. this is a consequence of its ‘Langevin’ character. • If µα / µ β ≤ 1 (Anthracene‘s case) recombination proceeds throughout the film volume. If µα / µ β >> 1 recombination is limited to a layer of thickness w ~ 2D/3( µα / µ β ) near the β injecting contact or if surface quenching of the exitons is efficient.3.88 µ and if one mobility is much larger than the other. if the two mobility are equal (to µ). If the minority carrier mobility is small ( µα / µ β >> 1 ) recombination is complete. If r = 1. In the Langevin’s case. so recombination is always efficient. We propose several conclusions follow: • r < 2/3 always. The injected current in the frame of the simplified theory and neglecting trapping effects. this may be a problem. 2. Double – injection (bipolar) bulk – limited current The case treated above is the one in which the minority current is injection – limited and small. The recombination yield is not very dependent on the transport properties. whatever the actual mobility.

4. 2. unless the mobility ratio µα / µ β >> 1 . Thermionic injection currents in organic materials The difference between semiconductors and organic solids may be expected here as well. The above conclusions remain approximately valid. The relative importance of these two factors depends on the position in the film. Electrode – limited currents If the majority carrier current J α is smaller than its SCL value. In other words. while the electron transit time has become very long and if J α ≥ µ β / µα J αSCL . One easily understands that it is still possible to have total recombination of the minority carriers. equation (5) becomes γ r ≈ eµ + / εε 0 and it not much affected by the small value of µ − . then nα < nα everywhere.5. It may be useful to first 24 .5. So τ t (β ) is larger than the SCL value given in equation (2). is injection limited. The recombination efficiency at constant minority carrier current is smaller.e. the double injection current is never much larger of the two possible unipolar SCL current. recombination is very probable. recombination is very inefficient. Indeed. they are supported by numerical calculations in the double injection case.5.Study of optical and electroluminescent properties of conjugated polymers instance µ h >> µ e . based on their different transport properties. It provided that their mobility is small enough compared to that of the majority carriers: If µ + >> µ − . no injected plasma can be formed the double injection current is limited by a combination of recombination and space charge. 2. In this case one may write: J α = eµα nα V V2 << εε 0 µα 3 L L (17) And the ratio of recombination time to transit time becomes: J α µα + µ β J αSCL µβ = J α ⎛ µα ⎜1 + J αSCL ⎜ µ β ⎝ ⎞ ⎟ ⎟ ⎠ (18) So. µ eff ≈ µ h or if recombination coefficient is given by Langevin formula. i.

If an externally applied voltage generates at the interface a field Ei. transport).e.Study of optical and electroluminescent properties of conjugated polymers recall how the saturation injection current Jsat at a metal – semiconductor interface can be obtained. At a metal-organic interface.EF the barrier height. Nc the conduction band density of states and φ =EC . Using again a detailed balance argument. the existence of an image potential at the interface decreases the barrier ⎛ eE ⎞ height by an amount ∆φ = e⎜ 1 ⎟ ⎜ εε ⎟ ⎝ 0⎠ 1/ 2 .the Schottky effect – leading to a current – voltage relation: J sat ⎛ φ ⎛ eE ⎞1 / 2 ⎞ ⎛ φ ⎞ ⎜ i⎟ ⎟ = AT exp⎜ − ⎟ exp⎜ − ⎜ kT ⎜ εε 0 ⎟ ⎟ ⎝ kT ⎠ ⎝ ⎠ ⎠ ⎝ 2 (21) this derivation implicitly assumes a large carrier mean free path (i. Jsat is equal to the current Jth of thermal carriers crossing the interface from the semiconductor side: J sat = J th = 1 1 ⎛ φ ⎞ encoυ th = eυ th N c exp⎜ − ⎟ 6π 6π ⎝ kT ⎠ (19) nco is the carrier concentration in the conduction band of the semiconductor. Recombination at an anthracene. Using for υ th and Nc the value for parabolic energy bands and the effective mass of carrier m* = m. 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. not diffusive. J sat becomes equal to the recombination current at the interface for carriers coming from the organic side. ballistic. 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.electrolyte interface and saturation currents for injection by such as an interface has been shown to conform quite well to such a 25 . This criterion is far from been fulfilled in OLEDs. one recovers the familiar relation: ⎛ φ ⎞ J sat = AT 2 exp⎜ − ⎟ ⎝ kT ⎠ (20) with A = 120A/cm2K2 . υ th their thermal velocity.

6.1. leading to correspondingly smaller saturation currents and less efficient injection above the image potential barrier. electron – injection and transport materials and emitting materials. while the EL efficiency is limited by the probability of creating non – radiative triplet excited states in the electron – hole recombination.Study of optical and electroluminescent properties of conjugated polymers model. For instance. taking reasonable values such as N s = 1021 and µ = 10-5 cm2/Vs yields a constant smaller than 10-2A/cm2K2. This is very low value. But the image potential very close to the metal surface extends below its Fermi level.6 for both types of materials. 2. is associated to the transport properties of the organic layer. The ideas have been recently applied to metal – organic interfaces. The organic emitting materials The advantages of organic materials over inorganic materials are their excellent color gamut and high fluorescence efficiency. 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. MATERIALS The materials using in OLEDs are divided into three types: hole – injection and transport materials.6. Many materials show intense photoluminescence with near unity quantum yield. Two types of OLED are usually considered differing by the nature of the ‘active’ emitting material: either it consists of ‘small’ conjugated molecules. J sat is still given by equation (15) but the constant is now much smaller. 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. choosing examples of 26 . Examples of molecular formulae are given in Fig. often metal chelates such as AlQ3 (8-hydroxyquinoline aluminum) or of conjugated polymers such as PPV. PVK … and their derivatives. 2. further decreasing the injection efficiency.

In this case. The conjugated entities are one-dimensional (1D) polymer chains. intrachain interactions are typically 2 orders of magnitude stronger than inter-chain ones. and red or red-orange. but also of ‘molecularly doped’ nonconjugated polymers (that is. These two types differ electrically in their energy level schemes and transport properties. entangled into an amorphous or at least highly disordered solid. zero-dimensional (0D). containing a dispersion of fluorescent dye molecules) and (more important for OLEDs) of such polymers bearing conjugated side-group. and by Marsitzky et al. This is the case of course of small molecules. the solid is then only weakly anisotropic.Study of optical and electroluminescent properties of conjugated polymers emitters in the blue. and the solid may have locally very anisotropic properties. which are of the Van der Walls type. 27 . they interact essentially via weak van der Waals forces. From the point of view of physics one should rather consider the following two classes of materials. green. Conjugated polymers are reviewed in this issue by Martin et al. and quite rigid. In the solid. The conjugated entities are small.

the fluctuations of the latter in the solid. 1D energy bands several eV wide. The gap between hole and electron conducting states is large and essentially empty (except for chemical impurities).Study of optical and electroluminescent properties of conjugated polymers Fig. interaction energies are very small compared to electronic transition energies. the situation is less clear. This is often described by a simple model in which the extended conjugation of the perfect chain is broken 28 . This is indeed observed in the only case where regular chains can be made. emitting in the blue (upper row). green (middle) and red or red-orange (bottom) In the 0D case. the polydiacetylenes. The large intra-chain coupling would generate. Disorder strongly localizes the electronic states. In the 1D case. Many band structures of conjugated polymers have been calculated. hence the energy spread of hole. conducting states remain small as well (a few tenths of eV at most). or electron. Example of conjugated polymer. in a perfectly regular chain.6.

4’. The total energy spread of the assembly of disordered chains remains large. Each segment is then taken as a box and its excited states energies will be higher the smaller the box (the ‘conjugation length’ model).6.4%. The addition of Ag into Mg considerably improves its chemical stability in the atmosphere and increases its sticking coefficient onto Alq3 upon deposition.LiF/Al films The bilayer cathode (LiF/Al) has been applied to various organic materials to form an effective electron injector.2. a blue OLED with a LiF/Al cathode on an emissive/electron – transport layer of 4. the polymer situation differs somewhat from that of the small molecules. b. For instance. Although this picture is over schematic.1’-biphenyl (DPVBi) had an external quantum efficiency of 1.bis(2. Thus.2 . hence for carrier injection. certainly the states span a large energy range and most of them are localized. These differences will be of consequence for interface levels at the metal-organic interface. a variety of low work – function metal alloys such as Mg – Ag and Al – Li are used. a. but most electron or hole states are localized and transport occurs by hoping between boxes. 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. Because of this large width. 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. which 29 . Li – Al films It is low work – function and considered as an effective cathode to achieve efficient electron injection in OLEDs.diphenylvinyl)1. c . 2.Study of optical and electroluminescent properties of conjugated polymers into shorter segments of various lengths.

Their emission must be in the visible. In such Ag PVK ITO Glass materials. It is a degenerate n-type semiconducting material that has wide applications in optics and optoelectronics.Study of optical and electroluminescent properties of conjugated polymers represented a 50 – fold increase in the device efficiency compared to a device with an Al only cathode. 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. The applications considered for organic electroluminescence are mostly in display.7. heat reflecting mirrors.7. High electrical conductivity ( ≈ 2 x 10-4 Ω -1 cm-1) and high transparency ( ≈ 90% in the visible spectrum range) of this material have been the focus of research throughout the world. DIFFERENT TYPES OF OLED 2. and heterojunction solar cells. 2.6.7. 2. Although ITO has the virtue of optical transparency but it is not a well – controlled material. The materials for Anodes The material for anode is widely ITO (Indium tin oxide). the electron and the hole conducting levels will be typically 2-3 eV and 5-6 eV respectively below the 30 Fig. 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. Structure of single OLED . Several alternative materials have been recently examined as anodes. a photon energy < 3 eV requires that the emitting materials be conjugated molecules or polymers.3.1. however all suffer from some unfavorable characteristics. These applications include flat panel display devices. electron beam deposition and chemical vapor deposition. from simple signs to large area TV screens.

The electron and hole conducting layers in the bulk are drawn as well defined and the internal electric field is assumed to be constant. For several reasons.87 eV) or Mg/Ag alloy (W = 3.Study of optical and electroluminescent properties of conjugated polymers vacuum level corresponding to the electron affinity and the ionization potential of the material. On the other hand. The energy levels in an OLED operating under forward bias and assuming thermionic injection at both electrodes. with W ~ 4. This is not a single energy level such as the HOMO or LUMO of an isolated molecule: intermolecular interactions generate bands. so the problem is not easily solved. It is a degenerate n –type semiconductor of high conductivity. with a gap larger than 3. 31 . The cathode and anode must inject into these levels.5 eV. such a figure is illustrative only. For thermionic injection to occur. But the organic layer is essentially amorphous and energy band tails should be presented. They are almost always important in insulators and any localized level that could lead to Schottky barrier formation. is an ITO layer on glass. through which the emitted luminescence can leave the diode.66 eV for Mg).9 eV. So it is transparent throughout the visible range. Choice material are presently calcium (W = 2. are usually drawn in the literature as on Fig. Neither can be actually correct.7. A convenient transparent anode. At the cathode for thermionic injection to be efficient. depending on the surface treatment ITO. assuming that constant field amounts to neglect space-charge effects.7 – 4. a low – W metal is required but such metals are quite reactive. evidence for Schottky barriers in OLEDs has remained scarce. the anode material should then have a large work – function W. In fact.

the converse.5 ± 0. electrodes may operate in other regimes than the thermionic injection one implied by the small contact barriers shown. for single polymer layer devices there are two ways to optimize injection. One way around the difficulty is to modify the electrodes by suitable layers 32 .Study of optical and electroluminescent properties of conjugated polymers Fig. Also. Al has been used quite often as a cathode. So.2 eV.2. These conditions are contradictory with the requirement that exiton emission should occur in the visible at 2. Multilayer diodes In order to get good thermionic injection at both electrodes in a single layer divice. 2. the organic material should have a large electron affinity Ac ≥ 3 eV and a small ionization potential I c ≤ 5 eV.The simplest model of an OLED made of a single organic layer between two injecting At the interface. This suggests the presence of a barrier layer or interface states at the electrode. The first is to select electrode materials with work-functions that match the electron affinity and ionization potential of the polymer layer.7. despite its larger work – function W = 4.5 eV. the figure implies a negligible effect of interface states or layers.8. is to tune the polymer energy levels to match to the work-functions of electrode. And the second. Indeed.5 eV. as the exiton energy is the gap energy E g = I c − Ac minus the exiton binding energy ~ 0. the relative energy level positions may be not be as show. for instance in the first polymer LED made.

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

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

the polymer – polymer interfaces are quite different from those including small molecules only.Study of optical and electroluminescent properties of conjugated polymers The second. In spin – coating. 35 . Which microscopic structure is at present unknown and recombination will take place within such layers. 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. even if the already deposited polymer is not soluble in the solvent used to deposit the overlaid layer. pulsed injection experiments have shown striking differences between the transient behaviors of small molecules and polymer bilayer diodes. Indeed.

Various deposition techniques such as sputtering. etc. sol – gel processes and electron beam evaporation have been used to produce ITO films. 11 showed the scheme of vacuum equipment combining an electron gun where 36 . • Vacuum evaporation: Alq3 used as emitter and Al or Ag used as cathode 3. thus creating the appropriate conditions for depositing the films • By using multiple crucibles. some different films can be deposited successively Fig. 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. The electron beam evaporation technique is a promising method for producing ITO films with lower resistively and higher transmittance. is a simple technique but it has also some limitation in evaporation of materials with a high temperature of vapor phase. Ta.Study of optical and electroluminescent properties of conjugated polymers CHAPTER III. 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. Mo. Thermal evaporation (TE) using resistive boats like W.1. SAMPLE PREPARATIONS AND EXPERIMENT 3. spray pyrolysis.1. 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.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.

The deposition power can be reached by adjusting the high voltage (U) up to 10 kV and the cathode current heating the filament. Resistance boats of Ta and W were used. The scheme of vacuum equipment combining an electron gun 3. Alq3 and Al/Ag films LiF.11.1. 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. Fig. respectively for LiF. Alq3 amd Al or Ag coatings were successively evaporated in a VHD3D unit with a vacuum as high as 10-5 Torr.3. Alq3 and metallic Al/Ag.Study of optical and electroluminescent properties of conjugated polymers electron beam are created from a tungsten filament and focused onto the crucibles by controlling the electric parallel magnets. The thickness of the LiF layer 37 . PVK and MEH-PPV The PVK and MEH-PPV powders were prepared in solution with pure cloruaform and xylene. and then attached to a surface of the spin-coating set-up. The solutions were put onto glass or ITO substrates. respectively.2.

38 . I – V characteristic curves to analyze the electrochemical properties of the deposited films. Here we used PU – H1 potentiostat in conjunction with a PU – H1 universal programmer. Micro – Raman spectra were recorded by using a multichannel Raman spectrometer (RAMLAB – 1B). 2 cm-1. In stretching mode extends between 1100 and 3000 cm-1. Under these conditions. According to the shape of these curves as well as oxidation and reduction peaks.Study of optical and electroluminescent properties of conjugated polymers was as low as 10 to 30 nm. the thickness of Alq3 layer is about 100 nm. Cyclic voltametry Cyclic voltametry determine the electrochemical current – voltage (IV) characteristics of an electrochromic electrode and device. SCE) and counter electrode (Pt grill) were used.2. A typical voltametry is diagrammed in Fig.2. one showed the mathematical decomposition of spectra and allowed a semiquantitative description of the films. Fe). for instance. A standardization of spectra was shown to give relevant results. reference electrode (SSE.2. A standard three – electrode configuration including working electrode (ITO. the stability the films under the light was checked previously. 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. 12 . 3. a wave number range extending ≈ 700 cm-1 was investigated at each scan. Concerning RS. with 632. The wave numbers can be considered as given with a precision not better than ca. we can describe the mechanisms of polymerizing processes. 3. The time necessary for a spectral acquisition was generally 3 min 20s. The mathematical decomposition of spectra is made using Spectra Calc software.2. The other evaporated films have been much thicker. Al/Ag – is about 200 nm.1.5 nm Hellion laser line. Raman spectrometer Raman spectroscopy (RS) gives relevant information about the mechanisms in polymers. CHARACTERIZATION METHODS 3.

Study of optical and electroluminescent properties of conjugated polymers Fig. Electron beams having energies ranging from a few thousand to 50 keV. 12 Experimental set – up for I – V measurement 3. Through continuous random scattering events.2. The result is a distribution of electrons that manage to leave the specimen. target X – rays are emitted and other signals such as light. 13. the SEM is perhaps the most widely employed thin – film and coating characterization instrument.3. with 50 keV a common value. heat and specimen current are produced and the sources of their origin can be imaged with appropriate detector. A schematic of the typical SEM is shown in Fig. 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. Scanning electron microscopy Because seeing is reliable and understanding. 39 . In addition. Upon impinging on the specimen. the primary beam effectively spreads and fills a teardrop – shaped interaction volume with a multitude of electronic excitons. are utilized. 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). the primary electrons decelerate and in losing energy transfer it inelastically to other atomic electrons and to the lattice.

Scheme of the scanning electron microscope 40 .Study of optical and electroluminescent properties of conjugated polymers Fig. 13.

The PPV polymer emits blue light (with wavelength of ca.Study of optical and electroluminescent properties of conjugated polymers CHAPTER IV. Poly(N-vinylcarbazole) (PVK) is not only a photoconductive polymer but also a photoluminescent one. PVK has some advantages. An active layer. so-called MEH-PPV.4-phenylene vinylene). Chemical synthesis of MEH-PPV followed a similar procedure as described by Wudl and the MEH. These properties are well known for a long time but since electroluminescent devices and organic light emitting diodes (OLED) have been achieved. consequently to obtain a higher electroluminescent efficiency of the OLED. 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. Ag vacuum-evaporated coating (50 nm thickness) is served as cathode. whereas MEH-PPV can emit light from blue to green color. thermal annealing was used. OLED WITH STRUCTURE OF ITO/MEH –PPV/Ag In this structure. 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. 4.2. In the structure with two carriers. ITO is used as an anode. 480 nm). Transparent electrically conducting films ITO were deposited by electron beam technique. for instance. electrons have the lower mobility and hence limit the current conduction process.PPV precursor was synthesized by the conventional Wessling method. the work function is matched to ITO and PVK film is easy deposited by vacuum evaporation using tantalum resistance 41 . a metallic layer. transmittance in visible range is high. the PVK thin films are under studies.5-(2'-ethylhexyloxy)-1. a prospective emitter is poly(2-methoxy. RESULTS AND DISCUSSION 4. To enhance workfunction of the ITO films.1. and the last. depending on the conjugation ratio between MEH and PPV compounds.

4. 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.1 cm2. the HOMO level of the HTL is located above the valence band of the polymer and below the Fermi level of the ITO. MEH-PPV films onto ITO and PVK were casted in nitrogen with thickness of ca. i. So.e. Preparation of ITO/MEH – PPV/Ag has been presented above. This spectrum is completely consistent with that of the standard PVK. Moreover.1.Study of optical and electroluminescent properties of conjugated polymers boats. However. The thickness of ITO films was measured on the cross-sectional micrographs made by using a LEICA “STEREOSCAN 440” electron scanning microscopy to reveal. Raman scattering measurements were carried out on a Dilor Jobin-Yvon Spex LAMBRAM -1B Raman scattering spectrometer. Resistivity (ρ) of the films was then determined through the experimental data of the sheet resistance (R ) and measured thickness (d). Hole transport layer (HTL) PVK Fig. fields. Many previous works. we have a diode of the structure like ITO/PVK/MEHPPV/Ag. 1 µm and active area of 0. 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. have been shown that to improve the stability and efficiency of OLEDs it is important to decrease the operating bias voltages.14 shows the Raman spectra the PVK thin film. 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. because with such a high hole mobility of PVK. By introducing PVK layer between the anode (ITO) and the polymer (MEH-PPV) one can reduce the barrier height. so that the power consumption and hence the Joule heating of the devices is reduced. for instance [10].2. PVK itself is a photoluminescent (PL) material. Potentiostat PGS-30. IV characteristics were measured using an Autolab. 42 .

the bands at 1170. 1170.14. 1546 and 1583 cm-1 . 1583 and 1624 cm-1) of PPV two bands at 1326 and 1624 cm-1 characterize vibration of vinylene group. 1582 and 1624 cm-1 in Fig.aromatic cycles. 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.) 300 200 1 100 2 0 0 300 600 900 1200 -1 1500 1800 Wavenumber (cm ) Fig. 965. 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. Raman spectra of PVK thin film 4. The PPV is a polymer combining intermediate 43 .Study of optical and electroluminescent properties of conjugated polymers 500 400 1): PVK powder 2): PVK/ITO thin film Intensity (a. 1326. 1283.u.2. Among Raman bands (963.2. 1546.15 for all the samples. 1310. 1414. 1113.

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. By applying a PVK as 44 . ITO as anode and Ag as cathode. Electrical property (I .2.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. 15 The Raman spectra of MEH – PPV thin film 4. it can be seen as a copolymer of acetylene and benzene. 16 there are present plots of the Current-Voltage (IV) characteristics of a three.Study of optical and electroluminescent properties of conjugated polymers structure between polyacetylene and polyphenylene. 1400 1200 1000 Intensity (a.MEH-PPV film '2' .3.MEH-PPV powder 800 1 600 400 200 2 0 400 800 1200 Wavenumber (cm ) -1 1600 2000 Fig.layers and a four-layers OLEDs. In Fig.u) '1' .

6 1.2 V. the electric field required for the onset of the current in the forward direction is decreased. 16 The I-V characteristic of ITO/PVK/MEH-PPV/Ag and ITO/MEH-PPV/Ag 45 .2 : ITO/PVK/MEH-PPV/Ag : ITO/MEH-PPV/Ag Current (mA/cm ) 2 0.0 -0. These electrical field values are corresponding to bias voltages of 12. 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.5 V and 17. 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.Study of optical and electroluminescent properties of conjugated polymers HTL between ITO and MEH-PPV.4 0.4 -20 -10 0 10 20 30 40 Electric field (MV/m) Fig. respectively for the four-layers and the three-layers OLEDs. 1.8 0.

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. 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.4. 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. Discusion OLEDs have been prepared from multiple layers: the ITO as anode was made by electron beam deposition followed by post-annealing. ITO. Both the PVK and the MEH-PPV films obtained have the same Raman characteristic bands of the initial powder.Study of optical and electroluminescent properties of conjugated polymers 4. 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. 4. PVK played a role of a hole – transport material. So it can have higher possibility of emissive recombination of excitons in the devices. OLED WITH STRUCTURE OF ITO/PVK/Alq3/LiF/Al In OLED. PVK as HTL was spin-coated. Alq3 is used as both HTL and ELT. deposited on glass substrates have been treated by thermal annealing in order to improve their quality for use in the OLEDs. An onset voltage was obtained as low as 6. it is LiF and Al melt is used as cathode.2. MEH-PPV as an emitter was casted in dry introgen and silver thin film as cathode was vacuum evaporated.8 V for these devices and no reverse current was observed. HTL – Hole transport layer PVK .3. which emits in the green with a broad emission peaking at 530 nm. In this structure. In this multiply – layers diode ITO is used as a transparent anode. Tris (8 hydroxyquinolinato) aluminum (Alq3) was used as an emissive material. In general. ELT – Electron transport layer. 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 .

1 to 1. using Ta resistance boats. From this figure one can note that: • The onset voltage of the device is rather low. and LiF have been prepared by vacuum evaporation. Various deposition techniques such as sputtering. 17a presents a typical IV-curve of the multiple-layer organic light emitting diode with ITO/PVK/Alq3/ LiF/Al structure. spray pyrolysis. the photoluminescence (PL) curve of the diodes exhibited these advantages in the current density of lighting Fig. These results strongly demonstrate the important role of the HTL and ETL in OLEDs. 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.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. sol – gel processes and electron beam evaporation have been used to produce ITO films. I-V characteristic of the device The super – thin layer (the thickness ranged from 0. Indeed.Study of optical and electroluminescent properties of conjugated polymers light. it consists of only 6. 17b. Fig. 5N-pure aluminum wire has been used for evaporation from W-basket boats. the replacement of In3+ by Sn4+ affects the optical and electrical properties of the ITO films. Alq3. The replacement produces free electrons that contribute to enhancing the conductivity. The electron beam evaporation technique is a promising method for producing ITO films with lower resistivity and higher transmittance. It is seen from this figure that 47 . All the films such as PVK. Alq3 and LiF crystalline powders which were purchased from Aldrich Ltd. In the In2O3 crystalline structure. This contact improves the electron transport from the high workfunction cathode into the emissive layer.0 nm) LiF has formed a shallow contact Al/LiFAlq3 instead of AlAlq3.3. Chemical pure produces.1. Aluminum coatings used as cathode with thickness of 100 nm were evaporated onto the polymer and composite films. 4. Initial materials for evaporation were of PVK.

5 2. nA/cm2 5 Current density (µΑ/cm2) Current density (nA/cm2) -1 0 1 2 3 4 5 6 7 8 2. 17.5 6 4 2 0 -2 -4 -6 -8 Voltage (V) Voltage (V) a). 48 .5 0.8 V for these devices. 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.0 1.Study of optical and electroluminescent properties of conjugated polymers although the diode emitted with a small current density. the PL curve has such a high abrupt increase in the intensity that.5 1. if it is possible to maintain. For these devices a PL-current density of 6 nA/cm2 has been reached. 3. and no reverse current was observed. The enhancement in both the onset electric field (onset voltage) and the reverse current has been obtained. Fig. This is just needed to carry-out further investigation of both the preparation techniques and capsulation in a much cleaner room. IV (a) and PL (b) characteristics of a multiple-layer OLED with ITO/PVK/Alq3/ LiF/Al structure 4.0 0.0 EL.0 4 3 2 1 0 -0. 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 explained due to the better injection of electrons from the Al-cathode into the emissive Alq3 material. one can expect a good lighting from the OLED.5 6 3. An onset voltage (Vons) was obtained as low as 6.3. namely 6 nA/cm2.2. b).

By introducing PVK layer between the anode (ITO) and the polymer (MEH-PPV) one can reduce the barrier height.4. 4. The measurement ITO/PVK+nc-TiO2/ Al was annealed at 200 0C in vacuum of 2 x 10-2 Torr for 2 hours. so that the power consumption and hence the Joule heating of the devices is reduced. 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. Both the PVK and PVK + nc-TiO2 composite films were prepared by spin coating method.75 was dissolved in monochrolobenzene by ultrasonic shaking. using two these solutions. fields.25 to 0.4. Mixture with a TiO2/PVK weight ratio (WR) ranging from 0. Aluminum coatings used as cathode with thickness of 100 nm were evaporated onto the polymer and composite films. To prepare PVK + nc-TiO2 composite films. Transparent electrically conducting films (ITO) were deposited by electron beam technique that can be seen elsewhere [3]. 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. To enhance workfunction of the ITO films. 18 shows the Raman spectra the PVK thin film onto ITO (PVK/ITO).Study of optical and electroluminescent properties of conjugated polymers 4. 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. because with such a high hole mobility of PVK. the HOMO level of the HTL is located above the valence band of 49 . for instance [5].1.e. i. thermal and chemical treatments have been used [4]. Many previous works. Raman spectra Fig. This spectrum is completely consistent with that of the PVK powders. have been shown that to improve the stability and efficiency of OLEDs it is important to decrease the operating bias voltages.

Study of optical and electroluminescent properties of conjugated polymers the polymer and below the Fermi level of the ITO.35) spin-coated film (B) 4. 500 A ) .P V K film B ) .4.) 300 A 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. However.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. studying the photoluminescent (PL) property of the films enables us to be aware of useful information about the 50 . while the PVK and the composite were deposited onto ITO coated glass. 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.u.C o m p o s ite film 400 Intensity (a.

Study of optical and electroluminescent properties of conjugated polymers polymer and the composite. An interesting result of this study is present in Fig. respectively called ELD and CELD. 19 Photoluminescent spectra of homogenous PVK (1) and nanocomposite (WR=0.3. It seems that 51 .P V K 2 ) . 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. 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.c o m p o s ite 2 0 0 0 1 0 0 0 1 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. 5 shows the plots of IV characteristics of the devices.35) spin-coated film (2) 4. 19 where there is observed a considerably large difference in the PL intensity between homogenous PVK and the PVK+ nc-TiO2 composite. 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 ) . Fig.4.

Study of optical and electroluminescent properties of conjugated polymers electrical behavior of the CELD exhibit a contrary way to the PL effect.P V K + T iO 2 Current (A) 1 0 .0 0 5 0 . 0 . 52 . 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.P V K 2 ) . while it is of 3 V obtained for the ELDs. 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. It is known that the reverse current increase strongly affect the diode performance. whereas in the ELDs this current starts increasing from the beginning. However.0 2 5 0 . 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.0 0 0 0 2 4 6 8 1 0 2 V o lta g e (V ) Fig. Fig.0 1 5 0 .0 1 0 1 ). 20 IV-characteristics of ITO/PVK/Al (ELD) (1) and ITO/PVK+nc-TiO2/Al (CELD) (2) diodes.0 2 0 0 .

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. 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. 53 . PVK and PVK + ncTiO2 films as emitter were spin-coated and aluminum thin film as cathode was vacuum evaporated. 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.Study of optical and electroluminescent properties of conjugated polymers 4.4.4. 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.

both the I-V and photoluminescent (PL) characteristics of ITO/PVK/MEH-PPV/ Ag devices have been enhanced. • By addition of PVK layer as hole transport layers between the ITO and MEH-PPV. Alq3 – by spin coating. • 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. 54 . Photoluminescent intensity (PL) of the composite has been much stronger (namely one order in magnitude) in comparison with a standard PVK film.TiO2 has been prepared by spin-coating. • A nanostructured composite film of PVK+nc. The result showed that the nanocomposite was formed as a polymeric matrix where the inorganic particles were surrounded by polymer. • Two types of organic light-emitting diodes have been prepared for study.Study of optical and electroluminescent properties of conjugated polymers 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. they are ITO/PVK/MEH-PPV and ITO/PVK/Alq3/LiF/Al where ITO used as anode has been produced by electron beam deposition. This effect is explained due to increase of emitting recombination possibility of excitons generated in the emissive layer. Ag. Al.

A.10 (1998) 7. Communications in Physics. Commun. Heeger.G.. Rev.. Long. Dinh. 1988 6.60:781 4..3.J. and Heeger.. N. N. and Su. P. Kivelson.J.1988. Organic field-effective transitors.D. 1977:578 2.Gurnee. Nguyen.. J. Mod. Horowitz.Williams R.Schrieffer. Phys. R. US Patent (1965) 5. Mai. S. 165 55 . P.Mater.Chem. H. Nigrey. W.H.H. A. Trung.1988.. L. Metal-Semiconductor Contacts. MacDiarmid.. A..G..J.R.Chem.P. Q. A. E. Adv. T. p. 60:781 3.. P. T..Commun. Oxford University Press. 13 (2003) No.J.Study of optical and electroluminescent properties of conjugated polymers REFERENCES 1.Ferander.. Rhoderick E.

.................3.................2......2............... DEVICE CONFIGURATION ....3....................7 1........5 1........................................................................12 2............17 2.....5........... OVERVIEW OF CONDUCTING POLYMERS .................................11 2................................. Doping of polyaniline by acid-base chemistry...................2.............16 2.........4.................................................19 2......5......................2......... Photon emission.............. Electrode – limited currents.............19 2................................................ Photon extraction .................................................1............................... Double – injection (bipolar) bulk – limited current...................................3......2.......2........................5.....................5...............11 2.... Current limiting factors......THE BASIC CONCEPT .................24 2......................5 1..............Study of optical and electroluminescent properties of conjugated polymers CONTENT Page ABTRACT.... CURRENT LIMITING FACTORS............................... ORGANIC LIGHT-EMITTING DIODE (OLED) ..2................................... THE CLASSIFICATION ....4................. INTRODUCTION... Chemical doping by charge transfer ....................4....... Electrochemical doping ................................9 CHAPTER II...............................5............. Thermionic injection currents in organic materials ...........2.........................20 2.18 2............ Unipolar bulk – limited (space – charge limited) current ..........1............6 1................................................5...............................22 2.........................23 2..............2..............3......................................................................................................3.....1....16 2......................3...5...................................20 2........................................................4..................... Carrier recombination.............1 INTRODUCTION . THE OPERATION ........3................................................................4 CHAPTER I.............................3.................1....24 56 ........................ Injection .....................1..............................4.................................................................................... Carrier transport ................................................ THE PARAMETERS.14 2........6 1.................5.. Photo-doping..................8 1..............................

....43 4...............................2.......41 4........................... OLED WITH STRUCTURE OF ITO/MEH –PPV/Ag ...... Mg – Ag metallic films .................................................... MATERIALS.. OLED WITH STRUCTURE OF ITO/PVK/Alq3/LiF/Al . RESULTS AND DISCUSSION..............................1.2................................44 4.....2...................................32 CHAPTER III......................................1................................................. Discusion ...................1..............6......................1...............47 57 ................................... Alq3 and Al/Ag films...................... The single of OLED...........36 3.............................3.. Li – Al films .......2............. CHARACTERIZATION METHODS.. SAMPLE PREPARATIONS AND EXPERIMENT ......................26 2........................................1..........29 2....46 4..........1....LiF/Al films..41 4................................ The materials for cathodes ................................. The organic emitting materials .........................7..........1..................... Scanning electron microscopy............2......3.....2................................................................. Hole transport layer (HTL) PVK ............2......36 3...7.........1.................................. The materials for Anodes ......38 3.39 CHAPTER IV..................................................... Transparent anode (ITO) .6... MEH – PPV emitting layer ......................................38 3.......................37 3.......................3...................................2.......3........................................2.....2.............................................................................30 2...Study of optical and electroluminescent properties of conjugated polymers 2...41 4................ OLED WITH STRUCTURE OF ITO/PVK/MEH-PPV/Ag.................................6... PVK and MEH-PPV ..1............... Multilayer diodes...........................29 b..............4...................................................V characteristic) . I-V characteristic of the device ....................... Electrical property (I ..........42 4. SAMPLE PREPARATION .....................................7.......3..46 4..................26 2.............1....................................... Cyclic voltametry .... Raman spectrometer....................2.2...........................29 c ...........................................36 3.................................2..............................37 3.............................................3........29 a......................2................................... DIFFERENT TYPES OF OLED .........30 2..............................38 3........................6......1........................................................30 2.................

............................................................. Discussion............................................................2......... I-V characteristics ............................................4.........48 4...............................53 CONCLUSION... Discussion................................................................................................................4.............3................................. Photoluminescent property ..................................................4........................4.........................1...........................49 4............Study of optical and electroluminescent properties of conjugated polymers 4...................3.....................54 REFERENCES ..51 4................................. Raman spectra.....50 4......4...............55 58 ............2.......................

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