ABSTRACT

The seminar is about polymers that can emit light when a voltage is applied to it. The structure comprises of a thin film of semiconducting polymer sandwiched between two electrodes (cathode and anode).When electrons and holes are injected from the electrodes, the recombination of these charge carriers takes place, which leads to emission of light .The band gap, i.e. The energy difference between valence band and conduction band determines the wavelength (colour) of the emitted light. They are usually made by ink jet printing process. In this method red green and blue polymer solutions are jetted into well defined areas on the substrate. This is because, PLEDs are soluble in common organic solvents like toluene and xylene .The film thickness uniformity is obtained by multi-passing (slow) is by heads with drive per nozzle technology .The pixels are controlled by using active or passive matrix. The advantages include low cost, small size, no viewing angle restrictions, low power requirement, biodegradability etc. They are poised to replace LCDs used in laptops and CRTs used in desktop computers today. Their future applications include flexible displays which can be folded, wearable displays with interactive features, camouflage etc.

INDEX

TOPIC 1) INTRODUCTION 2) SUBJECT DETAILING

2.1) CONSTRUCTION OF LEP 2.1.1) INKJET PRINTING 2.1.2) ACTIVE & PASSIVE MATRIX 2.2) BASIC PRINCIPLE & TECHNOLOGY 2.3) LIGHT EMISSION 2.4) COMPARISON TABLE

3) ADVANTAGES & DISADVANTAGES

3.1) ADVANTAGES 3.2) DISADVANTAGES

4) APPLICATION & FUTURE DEVELOPMENTS

4.1) APPLICATION 4.2) FUTURE DEVELOPMENTS

5) CONCLUSION 6) REFERENCES 7) APPENDICES

INTRODUCTION

Imagine these scenarios: - After watching the breakfast news on TV, you roll up the set like a large handkerchief, and stuff it into your briefcase. On the bus or train journey to your office, you can pull it out and catch up with the latest stock market quotes on CNBC. - Somewhere in the Kargil sector, a platoon commander of the Indian Army readies for the regular satellite updates that will give him the latest terrain pictures of the border in his sector. He unrolls a plastic-like map and hooks it to the unit's satellite telephone. In seconds, the map is refreshed with the latest high resolution camera images grabbed by an Indian satellite which passed over the region just minutes ago. Don t imagine these scenarios at least not for too long. The current 40 billion-dollar display market, dominated by LCDs (standard in laptops) and cathode ray tubes (CRTs, standard in televisions), is seeing the introduction of full-color LEP-driven displays that are more efficient, brighter, and easier to manufacture. It is possible that organic lightemitting materials will replace older display technologies much like compact discs have relegated cassette tapes to storage bins. The origins of polymer OLED technology go back to the discovery of conducting polymers in 1977, which earned the co-discoverers- Alan J. Heeger , Alan G. MacDiarmid and Hideki Shirakawa - the 2000 Nobel prize in chemistry. Following this discovery, researchers at Cambridge University UK discovered in 1990 that conducting polymers also exhibit electroluminescence and the light emitting polymer (LEP) was born!.

SUBJECT DETAILING
LIGHT EMITTING POLYMER

It is a polymer that emits light when a voltage is applied to it. The structure comprises a thin-film of semiconducting polymer sandwiched between two electrodes (anode and cathode) as shown in fig.1. When electrons and holes are injected from the electrodes, the recombination of these charge carriers takes place, which leads to emission of light that escapes through glass substrate. The band gap, i.e. energy difference between valence band and conduction band of the semiconducting polymer determines the wavelength (color) of the emitted light.

CONSTRUCTION Light-emitting devices consist of active/emitting layers sandwiched between a cathode and an anode. Indium-tin oxides typically used for the anode and aluminum or calcium for the cathode. Fig.2.1(a) shows the structure of a simple single layer device with electrodes and an active layer.

Single-layer devices typically work only under a forward DC bias. Fig.2.1(b) shows a symmetrically configured alternating current light-emitting (SCALE) device that works under AC as well as forward and reverse DC bias. In order to manufacture the polymer, a spin-coating machine is used that has a plate spinning at the speed of a few thousand rotations per minute. The robot pours the plastic over the rotating plate, which, in turn, evenly spreads the polymer on the plate. This results in an extremely fine layer of the polymer having a thickness of 100 nanometers. Once the polymer is evenly spread, it is baked in an oven to evaporate any remnant liquid. The same technology is used to coat the CDs. 2.1.1 INK JET PRINTING Although inkjet printing is well established in printing graphic images, only now are applications emerging in printing electronics materials. Approximately a dozen companies have demonstrated the use of inkjet printing for PLED displays and this technique is now at the forefront of developments in digital electronic materials deposition. However, turning inkjet printing into a manufacturing process for PLED displays has required significant developments of the inkjet print head, the inks and the substrates (see Fig.2.1.1).Creating a full colour, inkjet printed display requires the precise metering of volumes in the order of pico liters. Red, green and blue polymer solutions are jetted into well defined areas with an angle of flight deviation of less than 5. To ensure the displays have uniform emission, the film thickness has to be very uniform.

Fig. 2.1.1 Schematic of the ink jet printing for PLED materials For some materials and display applications the film thickness uniformity may have to be better than 2 per cent. A conventional inkjet head may have volume variations of up to 20 per cent from the hundred or so nozzles that comprise the head and, in the worst case, a nozzle may be blocked. For graphic art this variation can be averaged out by multi-passing with the quality to the print dependent on the number of passes. Although multi-passing could be used for PLEDs the process would be unacceptably slow. Recently, Spectra, the world s largest supplier of industrial inkjet heads, has started to manufacture heads where the drive conditions for each nozzle can be adjusted individually so called drive-per-nozzle (DPN). Litrex in the USA, a subsidiary of CDT, has developed software to allow DPN to be used in its printers. Volume variations across the head of 2 per cent can be achieved using DPN In addition to very good volume control, the head has been designed to give drops of ink with a very small angleof-flight variation. A 200 dots per inch (dpi) display has colour pixels only 40 microns wide; the latest print heads have a deviation of less than 5 microns when placed 0.5 mm from the substrate. . In addition to the precision of the print head, the formulation of the ink is key to making effective and attractive display devices.

The formulation of a dry polymer material into an ink suitable for PLED displays requires that the inkjets reliably at high frequency and that on reaching the surface of the substrate forms a wet film in the correct location and dries to a uniformly flat film. . The film then has to perform as a useful electro-optical material. Recent progress in ink formulation and printer technology has allowed 400 mm panels to be colour printed in under a minute. 2.1.2.ACTIVE AND PASSIVE MATRIX Many displays consist of a matrix of pixels, formed at the intersection of rows and columns deposited on a substrate. Each pixel is a light emitting diode such as a PLED, capable of emitting light by being turned on or off, or any state in between. Colored displays are formed by positioning matrices of red, green and blue pixels very close together. To control the pixels, and so form the image required, either 'passive' or 'active' matrix drive Pixel displays can either by active or passive matrix. Fig. 2.1.2 shows the differences between the two matrixes types, active displays have transistors so that when a particular pixel is turned on it remains on until it is turned off methods are used time. Active displays are preferred, however it is technically challenging to incorporate so many transistors into such small a compact area. The matrix pixels are accessed sequentially. As a result passive passive displays are prone to flickering since each pixel only emits light for such a small length of time. Active displays are preferred, however it is technically challenging to incorporate so many transistors into such small a compact area.

Fig: 2.1.2 Active & Passive Matrices In passive matrix systems, each row and each column of the display has its own driver, and to create an image, the matrix is rapidly scanned to enable every pixel to be switched on or off as required. As the current required to brighten a pixel increases (for higher brightness displays), and as the display gets larger, this process becomes more difficult since higher currents have to flow down the control lines. Also, the controlling current has to be present whenever the pixel is required to light up. As a result, passive matrix displays tend to be used mainly where cheap, simple displays are required. Active matrix displays solve the problem of efficiently addressing each pixel by incorporating a transistor (TFT) in series with each pixel which provides control over the current and hence the brightness of individual pixels. Lower currents can now flow down the control wires since these have only to program the TFT driver, and the wires can be finer as a result. Also, the transistor is able to hold the current setting, keeping the pixel at the required brightness, until it receives another control signal.

Future demands on displays will in part require larger area displays so the active matrix market segment will grow faster. PLED devices are especially suitable for incorporating into active matrix displays, as they are processable in solution and can be manufactured using ink jet printing over larger areas.

BASIC PRINCIPLE & TECHNOLOGY Polymer properties are dominated by the covalent nature of carbon bonds making up the organic molecule s backbone. The immobility of electrons that form the covalent bonds explain why plastics were classified almost exclusively insulators until the 1970 s. A single carbon-carbon bond is composed of two electrons being shared in overlapping wave functions. For each carbon, the four electrons in the valence bond form tetrahedral oriented hybridized sp orbitals from the s & p orbitals described quantum mechanically as geometrical wave functions. The properties of the spherical s orbital and bimodal p orbitals combine into four equal, unsymmetrical, tetrahedral oriented hybridized sp orbitals. The bond formed by the overlap of these hybridized orbitals from two carbon atoms is referred to as a sigma bond. A conjugated pi bond refers to a carbon chain or ring whose bonds alternate between single and double (or triple) bonds. The bonding system tends to form stronger bonds than might be first indicated by a structure with single bonds. The single bond formed between two double bonds inherits the characteristics of the double bonds since the single bond is formed by two sp hybrid orbitals. The p orbitals of the single bonded carbons form an effective pi bond ultimately leading to the significant consequence of pi electron de-localization. Unlike the sigma bond electrons, which are trapped between the carbons, the pi bond electrons have relative mobility. All that is required to provide an effective conducting band is the oxidation or reduction of carbons in the backbone. Then the electrons have mobility, as do the holes generated by the absence of electrons through oxidation with a dopant like iodine. 2.2.1. LIGHT EMISSION The production of photons from the energy gap of a material is very similar for organic and ceramic semiconductors. Hence a brief description of the process of electroluminescence is in order. Electroluminescence is the process in which
2 3 3

10

electromagnetic (EM) radiation is emitted from a material by passing an electrical current through it. The frequency of the EM radiation is directly related to the energy of separation between electrons in the conduction band and electrons in the valence band. These bands form the periodic arrangement of atoms in the crystal structure of the semiconductor. In a ceramic semiconductor like GaAs or ZnS, the energy is released when an electron from the conduction band falls into a hole in the valence band. The electronic device that accomplishes this electron-hole interaction is that of a diode, which consists of an n-type material (electron rich) interfaced with p-type material (hole rich). When the diode is forward biased (electrons across interface from n to p by an applied voltage) the electrons cross a neutralized zone at the interface to fill holes and thus emit energy. The situation is very similar for organic semiconductors with two notable exceptions. The first exception stems from the nature of the conduction band in an organic system while the second exception is the recognition of how conduction occurs between two organic molecules. With non-organic semiconductors there is a band gap associated with Brillouin zones that discrete electron energies based on the periodic order of the crystalline lattice. The free electron s mobility from lattice site to lattice site is clearly sensitive to the long-term order of the material. This is not so for the organic semiconductor. The energy gap of the polymer is more a function of the individual backbone, and the mobility of electrons and holes are limited to the linear or branched directions of the molecule they statistically inhabit. The efficiency of electron/hole transport between polymer molecules is also unique to polymers. Electron and hole mobility occurs as a hopping mechanism which is significant to the practical development of organic

11

Fig2.2.1 a demonstration of full conjugation of

electrons in PPV

Emitting devices. PPV has a fully conjugated backbone (figure 2.2.1), as a consequence the HOMO (exp link remember 6th form!) of the macromolecule stretches across the entire chain, this kind of situation is ideal for the transport of charge; in simple terms, electrons can simply "hop" from one orbital to the next since they are all linked. The delocalized electron clouds are colored yellow. PPV is a semiconductor. Semiconductors are so called because they have conductivity that is midway between that of a conductor and an insulator. While conductors such as copper conduct electricity with little to no energy (in this case potential difference or voltage) required to "kick-start" a current, insulators such as glass require huge amounts of energy to conduct a current. Semi-conductors require modest amounts of energy in order to carry a current, and are used in technologies such as transistors, microchips and LEDs. Band theory is used to explain the semi-conductance of PPV, see figure 5. In a diatomic molecule, a molecular orbital (MO) diagram can be drawn showing a single HOMO and LUMO, corresponding to a low energy orbital and a high energy * orbital. This is simple enough, however, every time an atom is added to the molecule a further MO is added to the MO diagram. Thus for a PPV chain which consists of ~1300 atoms involved in conjugation, the LUMOs and HOMOs will be so numerous as to be effectively continuous, this results in two bands, a valence band (HOMOs, orbitals) and a conduction band (LUMOs, * orbitals). They are separated by a band gap which is typically 0-10eV (check) and depends on the type of material. PPV has a band gap of 2.2eV (exp eV). The valence band is filled with all the electrons in the chain, and thus is entirely filled, while the

12

conduction band, being made up of empty * orbitals (the LUMOs) is entirely empty). In order for PPV to carry a charge, the charge carriers (e.g. electrons) must be given enough energy to "jump" this barrier - to proceed from the valence band to the conduction band where they are free to ride the PPV chain s empty LUMOs.(Fig. 2.2.2)

Figure 2.2.2 A series of orbital diagrams y A diatomic molecule has a bonding and an anti-bonding orbital, two atomic orbital gives two molecular orbitals. The electrons arrange themselves following, Auf Bau and the Pauli Principle. y A single atom has one atomic orbital. y A tri atomic molecule has three molecular orbitals, as before one bonding, one anti-bonding, and in addition one non-bonding orbital. Four atomic orbitals give four molecular orbitals. Many atoms results in so many closely spaced orbitals that they are effectively continuous and nonquantum. The orbital sets are called bands. In this case the bands are

13

separated by a band gap, and thus the substance is either an insulator or a semi-conductor. It is already apparent that conduction in polymers is not similar to that of metals and inorganic conductors; however there is more to this story! First we need to imagine a conventional diode system, i.e. PPV sandwiched between an electron injector (or cathode), and an anode. It is already apparent that conduction in polymers is not similar to that of metals and inorganic conductors ; however there is more to this story.

First we need to imagine a conventional diode system, i.e. PPV sandwiched between an electron injector (or cathode), and an anode. The electron injector needs to inject electrons of sufficient energy to exceed the band gap, the anode operates by removing electrons from the polymer and consequently leaving regions of positive charge called holes. The anode is consequently referred to as the hole injector. In this model, holes and electrons are referred to as charge carriers, both are free to traverse the PPV chains and as a result will come into contact. It is logical for an electron to fill a hole when the opportunity is presented and they are said to capture one another. The capture of oppositely charged carriers is referred to as recombination. When captured, an electron and a hole form neutral-bound excited states (termed excitons) that quickly decay and produce a photon up to 25% of the time, 75% of the time, decay produces only heat, this is due to the the possible multiplicities of the exciton. The frequency of the photon is tied to the band-gap of the polymer; PPV has a band-gap of 2.2eV, which corresponds to yellow-green light. Not all conducting polymers fluoresce, poly acetylene, one of the first conductingpolymers to be discovered was found to fluoresce at extremely low levels of intensity. Excitons are still captured and still decay, however they mostly decay to release heat. This is what you may have expected since electrical resistance in most conductors causes the conductor to become hot. Capture is essential for a current to be sustained. Without capture the charge densities of holes and electrons would build up, quickly preventing any injection of charge carriers. In effect no current would flow.
14

LIGHT EMITTING DIODES BASED ON CONJUGATED POLYMERS Conjugated polymers are organic semiconductors, the semiconducting behavior being associated with the molecular orbitals delocalized along the polymer chain. Their main advantage over non-polymeric organic semiconductors is the possibility of processing the polymer to form useful and robust structures. The response of the system to electronic excitation is nonlinear the injection of an electron and a hole on the conjugated chain can lead to a self-localized excited state which can then decay radiatively, suggesting the possibility of using these materials in electroluminescent devices. We demonstrate here that poly (p-phenylene vinylene), prepared by way of a solution-processable precursor, can be used as the active element in a large-area light-emitting diode. The combination of good structural properties of this polymer, its ease of fabrication, and light emission in the green-yellow part of the spectrum with reasonably high efficiency, suggest that the polymer can be used for the development of large-area light-emitting displays. There has been longstanding interest in the development of solid-state light-emitting devices. Efficient light generation is achieved in inorganic semiconductors with direct band gaps, such as GaAs, but these are not easily or economically used in large-area displays. For this, systems based on polycrystalline ZnS have been developed, although low efficiencies and poor reliability have prevented large-scale production. Because of the high photoluminescence quantum yields common in organic molecular semiconductors, there has long been interest in the possibility of light emission by these organic semiconductors through charge injection under a high applied field (electroluminescence). Light-emitting devices are fabricated by vacuum sublimation of the organic layers, and although the efficiencies and selection of colour of the emission are very good, there are in general problems associated with the long-term stability of the sublimed organic film against recrystallization and other structural changes. One way to improve the structural stability of these organic layers is to move from molecular to macromolecular materials, and conjugated polymers are a good choice in that they can, in principle, provide both good charge transport and also high quantum efficiency for the luminescence. Much of the interest in conjugated polymers has been in their properties as conducting materials, usually achieved at high levels of chemical doping, and there has been comparatively

15

little interest in their luminescence. One reason for this is that poly acetylene, the most widely studied of these materials, shows only very weak photoluminescence. But conjugated polymers that have larger semiconductor gaps, and that can be prepared in a sufficiently pure form to control non-radiative decay of excited states at defect sites, can show high quantum yields for photoluminescence. Among these, poly (p- phenylene vinylene) or PPV can be conveniently made into high-quality films and shows strong photoluminescence in a band centred near 2.2 eV, just below the threshold for to interband transitions. We synthesized PPV (I) using a solution-processable precursor polymer (II), as shown in Figure. This precursor polymer is conveniently prepared from dichloridep-xylene (III), through polymerization of the sulphonium salt intermediate (IV). We carried out the polymerization in a water/methanol mixture in the presence of base and, after termination, dialyzed the reaction mixture against distilled water. The solvent was removed and the precursor polymer redissolved in methanol. We find that this is a good solvent for spin-coating thin films of the precursor polymer on suitable substrates. After thermal conversion (typically 250C, in vacuo, for 10 h), the films of PPV (typical thickness 100 nm) are homogeneous, dense and uniform Furthermore, they are robust and intractable, stable in air at room temperature, and at temperatures >300C in a vacuum.

SYNTHETIC ROUTE TO PPV

Current-voltage characteristic for an electroluminescent device having a PPV film

16

70 mm thick are of 2 mm2, a bottom contact of indium oxide, and a top contact of aluminium. The forward-bias regime is shown (indium oxide positive with respect to the aluminium electrode). Structures for electroluminescence studies were fabricated with the PPV film formed on a bottom electrode deposited on a suitable substrate (such as glass), and with the top electrode formed onto the fully converted PPV film. For the negative, electron-injecting contact we use materials with a low work function, and for the positive, hole-injecting contact, we use materials with a high work function. At least one of these layers must be semi-transparent for light emission normal to the plane of the device, and for this we have used both indium oxide, deposited by ion-beam sputtering and thin aluminium (typically 7.15 nm). We found that aluminium exposed to air to allow formation of a thin oxide coating, gold and indium oxide can all be used as the positive electrode material, and that aluminium, magnesium silver alloy and amorphous silicon hydrogen alloys prepared by radio frequency sputtering are suitable as the negative electrode materials. The high stability of the PPV film allows easy deposition of the top contact layer, and we were able to form this contact using thermal evaporation for metals and ion-beam sputtering for indium oxide. Figure show typical characteristics for devices having indium oxide as the bottom contact and aluminium as the top contact. The threshold for substantial charge injection is just below 14 V, at a field of 2 106 V cm-1, and the integrated light output is approximately linear with current. Figure shows the spectrally resolved output for a device at various temperatures. The spectrum is very similar to that measured in photoluminescence, with a peak near 2.2 eV and well resolved phonon structure. These devices therefore emit in the green-yellow part of the spectrum, and can be easily seen under normal laboratory lighting. The quantum efficiency (photons emitted per electron injected) is moderate, but not as high as

17

reported for some of the structures made with molecular materials. The quantum efficiencies for our PPV devices were up to 0.05%. We found that the failure mode of these devices are usually associated with the failure of polymer/thin metal interface and is probably due to local joule heating there.

Integrated light output plotted against current for the electroluminescent device giving the current-voltage characteristic in Fig

Spectrally resolved output for an electroluminescent device at various temperatures.

The observation and characterization of electroluminescence in this conjugated polymer is of interest in the study of the fundamental excitations of this class of semiconductor. Here, the concept of self-localized charged or neutral excited states in the nonlinear response of the electronic system has been a useful one. For polymers with the symmetry of PPV, these excitations are polarons, either uncharged (as the polaron exciton) or charged (singly charged as the polaron, and doubly charged as the bipolaron). We have previously assigned the photoluminescence in this polymer to radiative recombination of the singlet polaron exciton formed by intra chain excitation and, in view of the identical spectral emission here, we assign the electroluminescence to the radiative decay of the same excited state. The electroluminescence is generated by recombination of the electrons and holes injected from opposite sides of the structure, however, and we must consider what the charge carriers are. We have previously noted that bipolarons, the more stable of the charged excitations in photo excitation and chemical doping studies, are very strongly self-localized, with movement of the associated pair of energy levels deep into the

18

semiconductor gap, to within 1 eV of each other. In contrast, the movement of these levels into the gap for the neutral polaron exciton, which one-electron models predict to be the same as for the bipolaron, is measured directly from the photoluminescence emission to be much smaller, with the levels remaining more than 2.2 eV apart. For electroluminescence then, bipolarons are very unlikely to be the charge carriers responsible for formation of polaron excitons, because their creation requires coalescence of two charge carriers, their mobilities are low and the strong self-localization of the bipolaron evident in the positions of the gap states probably does not leave sufficient energy for radiative decay at the photon energies measured here. Therefore, the charge carriers involved are probably polarons. The evidence that they can combine to form polaron excitons requires that the polaron gap states move no further into the gap than those of the polaron exciton and may account for the failure to observe the optical transitions associated with the polaron. The photoluminescence quantum yield of PPV has been estimated to be ~8%. It has been shown that the non-radiative processes that limit the efficiency of radiative decay as measured in photoluminescence are due to migration of the excited states to defect sites which act as non-radiative recombination centres, and also, at high intensities, to collisions between pairs of excited states. These are processes that can, in principle, be controlled through design of the polymer, and therefore there are excellent possibilities for the development of this class of materials in a range of electroluminescence applications. EFFICIENT LIGHT EMITTING DIODES BASED ON POLYMERS WITH HIGH ELECTRON AFFINITIES CONJUGATED polymers have been incorporated as active materials into several kinds of electronic device, such as diodes, transistors and light-emitting diodes. The first polymer light-emitting diodes were based on poly (p-phenylene vinylene) (PPV), which is robust and has a readily processible precursor polymer. Electroluminescence in this material is achieved by injection of electrons into the conduction band and holes into the valence band, which capture one another with emission of visible radiation. Efficient injection of electrons has previously required the use of metal electrodes with low work functions, primarily calcium; but this reactive metal presents problems for device stability. Here we report the fabrication of electroluminescent devices using a new family of processible poly (cyanoterephthalylidene) s. As the lowest unoccupied orbital of these polymers

19

(from which the conduction band is formed) lie at lower energies than those of PPV, electrodes made from stable metals such as aluminium can be used for electron injection. For hole injection, we use indium tin oxide coated with a PPV layer; this helps to localize charge at the interface between the PPV and the new polymer, increasing the efficiency of recombination. In this way, we are able to achieve high internal efficiencies (photons emitted per electrons injected) of up to 4% in these devices. 2.3 COMPARISON TABLE

This table compares the main electronic displays technologies. Each display type is described briefly, and the relative advantages and disadvantages are reviewed display type
Cathode Ray Tube

Acronym

Emissive or Reflective

Technology

Advantages

Disadvantages

CRT

Emissive

The CRT is a Very bright High (5kV to vacuum tube drive Wide viewing20kV+) using a hot voltages filament to angle No mask, so no Not a flat panel generate pixel size(rare thermolimitation for exceptions) electrons, mono Can be fragile, electrostatic and/or Minimum pixel particularly magnetic fieldssize 0.2mmneck-end to focus the (color) Heavy

20

electrons into a Low cost Source of X-rays beam attracted standard sizes unless screened to the high Low cost high- Affected by voltage anoderes color magnetic fields which is the Wide operatingDifficult to phosphor temperature recycle or coated screen. range dispose of Electrons colliding with Moderate the phosphor (20khrs+) life emit luminous radiation. Color CRTs typically use 3 electron sources (guns) to target red, green, and blue patterns on phosphor the screen. Liquid Crystal Display LCD Reflective An LCD uses Small, static, Backlight adds the properties mono panels cost, and often of liquid crystalscan be very low limits the useful in an electric cost life field to guide Both mono and Requires AC light from color panels drive waveform oppositely widely available Fragile unless polarized front and back display plates. The liquid crystal works as a helical director (when the driver presents the correct electric field) to guide the light through 90

21

from one plate

Polymeric Luminescent Material Development The design of luminescent materials for use in LED devices is as critical to device performance as the process of constructing the device itself. Processability, purity, thermal and oxidative stability , color of emission, luminance efficiency, balance of charge carrier mobility, and others are among many important materials properties required for a system to be viable in commercial LED device applications. Great strides have been made toward the development of new polymeric materials for luminescent applications .Although electroluminescent materials have been known for decades, and some were available for purchase in the early 1960s, they were limited until recently to inorganic semiconductors and small-molecule organic dyes. To be used in diode display devices, these materials require deposition as very thin films by vapor deposition or sublimation processes. Such processes are expensive, equipment intensive, and do not adapt well for coating large-area substrates .To overcome the device processing drawbacks of these emitting systems, a great deal of research has been focussed on the development of luminescent polymeric equivalents that offer the ability to coat substrates efficiently by any of a variety of common solution processes. A series of fluorescent polymers with extended conjugated backbones has emerged from this work. The year 1990 marked the discovery of the first electroluminescent polymer, PPV. [13] Since that time a variety of PPV derivatives with improved performance and processability have been developed. Other conjugated polymer systems such as polyfluorenes, polyphenylenes, poly (phenylene ethynylenes), and polyalkylthiophenes are also interesting emissive materials investigated over the past decade. Additional approaches to solutionprocessable polymeric emitting materials that have been explored include blending of inorganic semiconductors or organic dyes with polymers (inert and/or electroactive) as well as synthesizing polymers that bear discrete chromophores bound either pendant from or within the polymer backbone. Out of the host of materials investigated, two classes of polymers have emerged as leading candidates for PLED applications, the PPVs and the polyfluorenes. Through fine tuning of their chemical structures via polymerization variations, both of these
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polymer families have achieved ease of processability, high purity, and tenability of emission color. Many high-efficiency, high-brightness, and long-lived devices have been constructed from these materials. An excellent review of the state-ofthe-art in electroluminescent conjugated polymer development was published by Holmes and co-workers in 1998.[58] The reader is referred to this review for an extensive overview of the classes of polymeric materials that exist, and as a reference to many other previous reviews. A summary of the synthetic processes that yield the emissive polymers, materials properties reported, as well as device structures and performances derived from them are well covered, especially for the PPV family. Polyphenylenes, poly (phenylene ethynylenes), polyalkylthiophenes, and other polymer systems containing isolated chromophores either in the polymer chain or pendant to it are also briefly described. Polyfluorene homopolymers are lightly mentioned primarily due to the early stage of their development in 1998. In the past few years, much progress has been made within this class of material. The major groups of polymeric materials developed in the past decade will be summarized here. The discussion is by no means exhaustive (given the recent explosion of research in the field) and is limited to the groups of materials that have shown the greatest overall potential to date to be adopted as emissive materials in PLED applications: the poly (phenylene vinylene) s, the poly (fluorene) s, and the poly (phenylene) s, as illustrated in Figure 3. Polyfluorene homo- and co-polymers are intentionally highlighted since they have not been well reviewed in the past, much progress has been made very recently, and this class of material has quickly emerged as an extremely viable LED polymeric material of great commercial interest. Polyfluorene Alternating Copolymers Tertiary aromatic amines have been known as excellent hole-transport materials and have found utility in photoconductors and in LEDs. With the Pd-catalyzed polymerization process, it is possible to prepare high-molecular-weight, alternating copolymers consisting of 9,9 -dialkylfluorene and various aromatic amines. These alternating polymers are all blue emitters, excellent film formers, and soluble in conventional organic solvents. Films of these polymers show distinct and reversible oxidation potentials by cyclic voltammetry and can be cycled without any appreciable change. Hole mobilities of these amine copolymers are quite high (3 104 to 1 103 cm2/V s) [6466] equaling hole mobility values for small molecules such as tetraphenyl diamine (TPD) doped into polycarbonates. The high hole mobility of these materials suggests that they are

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potentially useful as photoconductors as well as hole transporters in LED devices. In light of the success in creating polymers with unique properties, the alternating copolymer approach has been extended to other conjugated monomers, as Figure 4 exemplifies (e.g., thiophene, bithiophene, triarylamine, etc.). All copolymers are of high molecular weight, they are highly photo luminescent, and their emissive colors can be qualitatively correlated to the extent of delocalization in the co monomers. For example, the thiophene copolymer emits bluish green light, the cyanostilbene copolymer emits green light, and the bithiophene copolymer emits yellow light. Thus, the choice of comonomer in the fluorene-based polymer family has served as an excellent synthetic tool for designing polymers with wellbalanced hole- and electron-transport properties and fine color control. A portfolio of fluorene copolymers that emit colors spanning the entire visible range has been prepared using the improved Suzuki route. [63] Rich red-, green-, and blue-emitting polymers are of highest interest. No other polymer class offers the full range of color with high efficiency, low operating voltage, and high lifetime when applied in a device configuration. Thus the polyfluorene based molecules are the most viable LEPs for commercialization; and since making these materials available, we have positive feedback from a variety of customers who have validated this concept to us. Poly (p-phenylene vinylene) and Derivatives Since the discovery about a decade ago of the ability of PPV to emit light (yellowgreen) under electrical stimulation, numerous research groups have continued to work towards optimization of this promising class of material. Improvements have developed primarily in ease of synthesis and processability, control of charge carrier balance, overall device power efficiency and lifetime, and to some extent emission wavelength tunability. A variety of solvent-processable precursor polymers (converted thermally to PPV following the coating process), solutionprocessable versions of PPV, and PPV copolymers (to facilitate electron injection and modulate color) have resulted from these efforts. The first convenient synthetic route to PPVs was first described by Wessling et al. in 1968 via bis sulfonium salt monomers. [14, 15] Since these original accounts, many variations on the theme have evolved. Routes have primarily afforded the ability to reproducibly generate high-molecular-weight, high-purity polymers, vary functional groups bound to the parent backbone (particularly solubilizing groups and groups to enhance electron affinity), and produce PPVs with improved efficiency in LED devices. The chemistry has remained somewhat restricted in

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enabling development of rich, saturated red and blue emitters, and the chemical structure of the PPV backbone is inherently photo-oxidatively unstable due to the vinylene linkages. While these issues are likely to continue to challenge the introduction of PPVs into commercial display devices (particularly multi- and fullcolor applications) in the future, significant progress has been made toward the optimization and tuning of these materials, making them very good candidates for PLED applications. POLYPHENYLENE Poly (1, 4-phenylene) (PPP) represents another class of conjugated polymer of interest to the PLED field. Wide band gaps are typical for PPPs and allow emission of blue light. Since the design of efficient long-lived blue emitters remains a significant challenge to the field, these polymers, like the poly fluorenes, are attractive candidates for consideration. As with the PPVs, most PPPs are insoluble and intractable. Thus, research activities in the PPP field have emphasized routes to PPP films via soluble thermally converted precursor polymers, as well as the development of soluble PPPs. A wide variety of processable PPP precursor routes have been described. [76] Similar to the PPV precursor chemistries, the PPP precursor routes typically involve the thermal elimination of a leaving group(s) to generate the fully conjugated system. For example, elimination of two equivalents of acetic acid (per monomer unit) from poly-1, 4-(5, 6-diaceto-2, 3-cyclohexene) enables aromatization of the polymer chain rings and formation of the PPP structure. Relatively high temperatures are required to effect the conversion, and side reactions that can lead to reduction of molecular weight (and reduce polymer film integrity) are problematic. Therefore, progress in the precursor approach to PPP emissive devices has been slow and has met with very limited success. A great deal of attention has been focused on the preparation and characterization of PPPs derived from monomers functionalized with a variety of solubility-enhancing groups, including alkyl, alkoxy, and aryl units, analogous to the development of soluble PPV systems. Since themonomers and resulting polymers are soluble if appropriately long or bulky substituents are employed, the polymerization reaction can occur in solution using well-known aryl or Suzuki coupling approaches. Molecular weights high enough to cast films with good integrity have been achieved, and blue-emitting diodes have been constructed and demonstrated reasonable efficiencies.

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Operational Characteristics: - The primary attributes of PLED device performance are its emissive ability or perceived brightness, color matching within targeted specifications, and control and longevity in operation. The term brightness is a physiological description describes the yellow-green portion of the spectrum to which of light intensity with respect to the wavelength sensitivity of the human eye. The average observer possesses daylight sensitivity to wavelength described by the photopic efficacy curve depicted in Figure. The maximum of this response curve to which we are most sensitive. The response is almost Gaussian, falling off rapidly towards either the red or blue. This photopic response has significant implications for the materials designer of light-emitting polymers. For a green emitter, a given number of photons corresponding to a proportional number of electronic transitions will be perceived as attaining certain brightness. For a red emitter, however, the material must support a significantly greater number of electronic transitions in the same time interval in order to be perceived at the same brightness level. For materials with similar quantum efficiencies, more emitted photons come at the expense of increased current, which is typically achieved at higher operating voltages. Matching similar operating characteristics and brightness levels require dissimilar material EL efficiencies. Color tuning is an important parameter when addressing the scope of LEPs. Due to the disorder of the polymer matrix, emission peaks will be broad, with a full width at half maximum (FWHM) approaching 60 to 70 nm for monochromatic sources. Color is calculated using the integral of spectral emission as a function of wavelength against the chromatic sensitivity of the eye. This results in a set of coordinates on a chromaticity graph defined by international standards maintained by the Commission International de l'Eclairage (CIE). Figure 6 illustrates typical PLED device data from two different color emitters, one red and the other green. Identical device structures were employed to duplicate conditions that are present on a multicolor display. Both devices utilize 40 nm of PEDOT as the HTL and 80 nm of the respective EML. Both devices also use calcium as the cathode contact. The green device has a maximum EL peak at 534 nm and the red device has its maximum emission at 634 nm. The color coordinates according to the CIE 1931 chromaticity diagram for the green emitter are (0.385, 0.579), and for the red emitter the CIE coordinates are (0.683, 0.313). A desirable feature with LEPs is that they can be fabricated into a device possessing a relatively constant efficiency over a wide luminance range. An example of the near-linearity of the material efficiency of the same green emitter described above is shown in Figure. The green emitter is more efficient, with higher luminance levels at lower voltage

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levels than can be achieved with the red emitter in an identical device configuration. If we approximate the relative EL spectral curves to follow the same shape, then according to the photopic efficacy model of the eye, the red emitter must produce four times more photons than the green emitter in the same period of time to stimulate an equal sensation of brightness. For deep-blue emitters, the relationship is less favorable. Lifetime reliability is also an important characteristic of this technology. Although different end-users have their own unique lifetime tolerances, we shall adhere to the current definition that lifetime refers to that duration of operating time corresponding to the decay of device luminance to one-half of the initial value. We shall also describe lifetime parameters that are obtained under DC (or continuously ON) conditions. When describing device lifetime, it is also important to specify the corresponding initial luminance level from which it is measured. For example, an early candidate for a polyfluorene- based red EL was measured for device lifetime, of which the results of one device are shown in Figure 8. The data were obtained using DC operation under constant current driving conditions. The initial luminance value was 100 cd/m2 and was directly proportional to the current applied to the device. Of interest are both the voltage rise with time. As well as the luminance decay. Varying the molecular design of EL polymers will permit long lifetimes, but with varying degrees of voltage change during the operational lifetime of a device. The lifetime of this specific device was later found to be approximately 5500 h. Such data were used to compile the engineering diagram shown in Figure 9. For the same red material, data were obtained from many DC lifetime evaluations starting with various initial luminances, all at room-temperature and -pressure conditions. None of the data were extrapolated; all data represent empirical observations of device performance in the laboratory. The relationship between initial luminance and lifetime follows an inverse power law very well; with L0 describing the initial luminance and T1/2 was representing the half-life. Note that lifetimes of 1 000 000 h are possible with this early material candidate with this specific device configuration, but only with an initial luminance value of 5 to 7 cd/m2. Such graphical relationships are essential to the design engineer considering certain performance levels over a desired operating duration .Electroluminescent material applied to a transparent surface and excited to emission creates a Lambertian source of light, in that the surface can be adequately described by the surface integral of a two-dimensional array of diffuse point emitters, each generating light equally. As such, potential applications that are replacements of filament-based sources of light are not straight forward,

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especially if product specifications are defined in terms of the luminous intensity of localized point emitters. In these circumstances, different means of describing product performance are required. Descriptions of filament bulb performance describe luminance intensity in units of candelas (cd), whereby surface emitters are described in terms of luminance with units in cd/m2. The two systems of photometric nomenclature can be reconciled by considering requirements need to be redefined. For example, the luminance intensity for some safety indicators is specified on the central optical axis, which is directly in-line with the filament source. It is implicitly assumed that there will be some intensity drop-off at other spatial locations on the front lens. The same intensity available at all points over an extended emitter would be perceived as uncomfortably bright, even though that is what would be required to meet the defining product specifications. Therefore, as this technology is considered for incumbent technology replacement, existing product specifications will need to be broadened to include Lambertian sources. Specific applications intended for the marketplace will require their own unique engineering and tooling. But given the commonality of the emissive medium, there are engineering aspects that are common to most application embodiments. Most applications of either monochrome or multicolor formats for information display will require pixilation of the emissive area. There are two primary methodologies associated with achieving this, and both require etching rows of ITO strips on the transparent substrate, and later depositing columns of cathode electrodes across the display. Where the cathode and anode overlap defines a pixel. Simple excitation of a given row and column defines passive-matrix operation. Passive-matrix driving schemes rely on pulsing each row of pixels in sequence where the entire display format is scanned with a period of less than 1/30 s. This corresponds to the limit of visual temporal resolution, otherwise known as the physiological persistence of the latent image. For a display built of N rows, each row will be pulsed (1/N)(1/30) s each. In that way, the observer will not notice image flicker and will perceive a continuous image display. The addition of individual thin-film transistors on the substrate for each pixel permits individual pixels to be independently turned on and off, and alleviates the need to raster each row sequentially within 1/30 s. This operation defines active-matrix driving. Fine display resolution is achieved with small, closely spaced pixels. For very fine resolution, neighboring pixels could be so closely spaced that interpixel communication could distort the intended operation with what is referred to as cross-talk. Cross-talk will result in a blooming effect whereby nearest neighbor pixels will display some unintended

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gray-scale activation state. The use of highly conducting polymers as the HTL can aggravate this problem by providing a low resistive path to nearest neighbor sites. This can be overcome by modifications to the conductivity of the HTL, or to the driver electronics, or both. In the passive matrix display, a pixel that will be in the active state for 1/N of the scan period and which is designed to be perceived at a luminance of L will have to be pulsed to a luminance of NL for (1/N) (1/30) s. In addition, improved image contrast from the display is achieved by using a polarizer front filter, which also reduces the perceived luminance by approximately 50 %. Therefore, a 64 128 pixel display running with a maximum perceived luminance of 100 cd/m2 will be designed to operate with a maximum luminance of 200 cd/ m2 (filter accommodation), and a given pixel will be required to emit with 12 800 cd/m2 for 0.5 ms every 33 ms. Such pixels may require 150 mA/cm2 given common materials characteristics. For portable displays with small pixel sizes operating under short pulse duration, this is not expected to introduce any undue Joule-heating effects. In fact, the pulsing operation will permit higher device efficiencies and luminance levels than would be achievable with DC (continuously ON) operation. [79] However, for large display formats where the number of rows is large, the pulsed requirements for a pixel can be substantial. For displays beyond approximately 6 inch (1 inch 2.5 cm) diagonal, active-matrix operation will be required. Then the minimum time for each pixel to be operated will be 1/30 s, and the maximum luminance will be the value required for observation (200 cd/m2 if used with a polarizer filter). It is expected that the product lifetime based on an active matrix operation will exceed that achievable with a passive-matrix drive scheme. Also common to PLED-based products will be the requirement for airtight device packaging. The PLED is a semiconducting optoelectronic device operating at fields near half a million volts per centimeter. With current flowing through the matrix, trapped chemisorbed water molecules can undergo electrolysis, liberating radical oxygenbearing ions, which are detrimental to organic molecules. The preferred methods of device encapsulation will have to stay below the glass transition temperature of the polymers, because going above this precipitates device shorts and failure. [80] Therefore, device encapsulation schemes are not likely to greatly exceed 100 _C. The engineering of flexible displays offers greater challenges, but comes with greater rewards. Some of the issues that will need to be addressed include providing a substrate that seals against moisture and oxygen, maintaining flexibility while maintaining the adhesion and integrity of a conducting anode, and accommodating an encapsulation scheme with package flexibility. Dow is

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uniquely positioned with access to a broad portfolio of materials expertise across the company to address these and related challenges that face the final stage of product definition.

3.1 ADVANTAGES y y y y Requires only 3.3 volts and have lifetime of more than 30,000 hours. Low power consumption. Self luminous. No viewing angle dependence.

y Display fast moving images with optimum clarity. y Cost much less to manufacture and to run than CRTs because the active material is plastic. y Can be scaled to any dimension. y Fast switching speeds that are typical of LEDs. y No environmental draw backs. y No power in take when switched off. y All colours of the visible spectrum are possible by appropriate choose of polymers. y Simple to use technology than conventional solid state LEDs and lasers. y Very slim flat panel. 3.2 DISADVANTAGES

y Vulnerable to shorts due to contamination of substrate surface by dust. y Voltage drops. y Mechanically fragile. y Potential not yet realized.

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APPLICATIONS & FUTURE DEVELOPMENTS

4. APPLICATIONS Polymer light-emitting diodes (PLED) can easily be processed into large-area thin films using simple and inexpensive technology. They also promise to challenge LCD's as the premiere display technology for wireless phones, pagers, and PDA's with brighter, thinner, lighter, and faster features than the current display. 4.1 PHOTO-VOLTAICS CDT s PLED technology can be used in reverse, to convert light into electricity. Devices which convert light into electricity are called photovoltaic (PV) devices, and are at the heart of solar cells and light detectors. CDT has an active program to develop efficient solar cells and light detectors using its polymer semiconductor know-how and experience, and has filed several patents in the area.

Digital clocks powered by CDT's polymer solar cells

4.2 POLY LED TV Philips will demonstrate its first 13-inch Poly LED TV prototype based on polymer OLED (organic light-emitting diode) technology Taking as its reference application the wide-screen 30-inch diagonal display with WXGA (1365x768) resolution,

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Philips has produced a prototype 13-inch carve-out of this display (resolution 576x324) to demonstrate the feasibility of manufacturing large-screen polymer OLED displays using high-accuracy multi-nozzle, multi-head inkjet printers. The excellent and sparkling image quality of Philips' Poly LED TV prototype illustrates the great potential of this new display technology for TV applications. According to current predictions, a polymer OLED-based TV could be a reality in the next five years.

4.3 BABY MOBILE BABY MOBILE This award winning baby mobile uses light weight organic light emitting diodes to realize images and sounds in response to gestures and speech of the infant.

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4.4 MP3 PLAYER DISPLAY Another product on the market taking advantage of a thin form-factor, lightemitting polymer display is the new, compact, MP3 audio player, marketed by Go Dot Technology. The unit employs a polymeric light-emitting diode (PLED) display supplied by Delta Optoelectronics, Taiwan, which is made with green Lumation light-emitting polymers furnished by Dow Chemical Co., Midland, Mich.

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5. FUTURE DEVELOPMENTS Here are just a few ideas which build on the versatility of light emitting materials.

High efficiency displays running on low power and economical to manufacture will find many uses in the consumer electronics field. Bright, clear screens filled with information and entertainment data of all sorts may make our lives easier, happier and safer.

Demands for information on the move could drive the development of 'wearable' displays, with interactive features.

Eywith changing information cole would give many brand ownerve edge

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The ability of PLEDs to be fabricated on flexible substrates opens up fascinating possibilities for formable or even fully flexible displays e catching packaging intent at the point of sa d s a valuable competition. FEW MORE DEVELOPMENTS Because the plastics can be made in the form of thin films or sheets, they offer a huge range of applications. These include television or computer screens that can be rolled up and tossed in a briefcase, and cheap videophones. Clothes made of the polymer and powered by a small battery pack could provide their own cinema show. Camouflage, generating an image of its surroundings picked up by a camera would allow its wearer to blend perfectly into the background A fully integrated analytical chip that contains an integrated light source and detector could provide powerful point-of-care technology. This would greatly extend the tools available to a doctor and would allow on-the-spot quantitative analysis, eliminating the need for patients to make repeat visits. This would bring forward the start of treatment, lower treatment costs and free up clinician time. The future is bright for products incorporating PLED displays. Ultra-light, ultra-thin displays, with low power consumption and excellent readability allow product designers a much freer rein. The environmentally conscious will warm to the absence of toxic substances and lower overall material requirements of PLEDs, and it would not be an exaggeration to say that all current display applications could benefit from the introduction of PLED technology. CDT sees PLED technology as being first applied to mobile communications, small and low information content instrumentation, and appliance displays. With the emergence of 3G telecommunications, high quality displays will be critical for

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handheld devices. PLEDs are ideal for the small display market as they offer vibrant, full-colour displays in a compact, lightweight and flexible form. Within the next few years, PLEDs are expected to make significant in roads into markets currently dominated by the cathode ray tube and LCD display technologies, such as televisions and computer monitors. PLEDs are anticipated as the technology of choice for new products including virtual reality headsets, a wide range of thin, technologies, such as televisions and computer monitors. PLEDs are anticipated as the technology of choice for new products including virtual reality headsets, a wide range of thin, lightweight, full colour portable computing, communications and information management products, and conformable or flexible displays.

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CONCLUSION

Light-emitting polymers have been studied intensively as materials for light emitting diodes (LEDs). Here research efforts toward developing these materials for commercial applications are reviewed. The Figure shows the preferred twolayer device structure for commercial polymer LEDs as well as polyfluorene, one of the polymers discussed. Light-emitting polymers (LEPs) to the unique class of aromatic organic molecules that exhibit semiconducting behavior and give off light when electrically stimulated. They are, consequently, electroluminescent as well as photo luminescent when stimulated by long-wave ultraviolet (UV) irradiation. Electro active devices based on LEPs typically operate at or below 5 V direct current (DC), have demonstrated high efficiencies in excess of 20 lm/W, and are approaching average operating lifetimes of 10 000 h at 200 cd/m2 intensity. As polymers, these materials exhibit mechanical, electrical, and luminescent properties that hold great potential for display application. The mechanical properties of polymers enable them to be cast in a variety of shapes and sizes, and their simplified processing offers fewer steps to manufacture, thereby providing economic advantages over many other more elaborate device fabrication techniques. Light is produced in the polymer by the fast decay of excited molecular states, the color of which depends on the energy difference between those excited states and the molecular ground level. A light-emitting device comprises a thin film structure of one or two layers typically no more than 0.1 lm thick, sandwiched between two electrodes.

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APPENDIX This report covers topics on Light Emitting Polymers. Polymeric electroluminescence (EL) is a phenomenon based on amorphous, disordered organic semiconducting materials that has stimulated technological activity across a wide interdisciplinary reach within academic, industrial, and governmental sectors. Efforts aimed at developing associated technology have created a rare opportunity to develop high value products and have contributed fundamental scientific insight in this area, which is poised for commercial success. Recent materials advances have endowed the concept of plastic light with the optical, electrical, and mechanical characteristics that truly make it disruptive technology within the display and lighting industries in that it is compatible with conventional device replacement and it offers new opportunities for exploitation. We review the materials science and engineering of this field within the framework of anticipated impact on product definition, as well as highlight contributions to the field originating from within The Dow Chemical Company.

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REFERENCES

1. www.google.co.in 2. Researches made by The Dow Chemical Company

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