OLED
An organic light-emitting diode, also known as organic electroluminescent 'diode', is a type of light-emitting diode in which the emissive electroluminescent layer is an organic compound film that emits light in response to an electric current. This organic layer is situated between two electrodes; typically, at least one of these electrodes is transparent. OLEDs are used to create digital displays in devices such as television screens, computer monitors, and portable systems such as smartphones and handheld game consoles. A major area of research is the development of white OLED devices for use in solid-state lighting applications.
There are two main families of OLED: those based on small molecules and those employing polymers. Adding mobile ions to an OLED creates a light-emitting electrochemical cell which has a slightly different mode of operation. An OLED display can be driven with a passive-matrix or active-matrix control scheme. In the PMOLED scheme, each row and line in the display is controlled sequentially, one by one, whereas AMOLED control uses a thin-film transistor backplane to directly access and switch each individual pixel on or off, allowing for higher resolution and larger display sizes. OLEDs are fundamentally different from LEDs, which are based on a p–n diode crystalline solid structure. In LEDs, doping is used to create p- and n-regions by changing the conductivity of the host semiconductor. OLEDs do not employ a crystalline p-n structure. Doping of OLEDs is used to increase radiative efficiency by direct modification of the quantum-mechanical optical recombination rate. Doping is additionally used to determine the wavelength of photon emission.
OLED displays are made in a similar way to LCDs, including manufacturing of several displays on a mother substrate that is later thinned and cut into several displays. Substrates for OLED displays come in the same sizes as those used for manufacturing LCDs. For OLED manufacture, after the formation of TFTs, addressable grids, or indium tin oxide segments, the display is coated with hole injection, transport and blocking layers, as well with electroluminescent material after the first two layers, after which ITO or metal may be applied again as a cathode. Later, the entire stack of materials is encapsulated. The TFT layer, addressable grid, or ITO segments serve as or are connected to the anode, which may be made of ITO or metal. OLEDs can be made flexible and transparent, with transparent displays being used in smartphones with optical fingerprint scanners and flexible displays being used in foldable smartphones.
History
and co-workers at the Nancy-Université made the first observations of electroluminescence in organic materials, in the early 1950s. They applied high alternating voltages in air to materials such as acridine orange dye, either deposited on or dissolved in cellulose or cellophane thin films. The proposed mechanism was either direct excitation of the dye molecules or excitation of electrons.In 1960, Martin Pope and co-workers at New York University developed ohmic dark-injecting electrode contacts to organic crystals. They further described the necessary energetic requirements for hole and electron injecting electrode contacts. These contacts are the basis of charge injection in all modern OLED devices. Pope's group also first observed direct current electroluminescence under vacuum on a single pure crystal of anthracene and on anthracene crystals doped with tetracene in 1963 using a small area silver electrode at 400 volts. The proposed mechanism was field-accelerated electron excitation of molecular fluorescence.
Pope's group reported in 1965 that in the absence of an external electric field, the electroluminescence in anthracene crystals is caused by the recombination of a thermalized electron and hole, and that the conducting level of anthracene is higher in energy than the exciton energy level. Also in 1965, Wolfgang Helfrich and W. G. Schneider of the National Research Council in Canada produced double injection recombination electroluminescence for the first time in an anthracene single crystal using hole and electron injecting electrodes, the forerunner of modern double-injection devices. In the same year, Dow Chemical researchers patented a method of preparing electroluminescent cells using high-voltage AC-driven electrically insulated one millimetre thin layers of a melted phosphor consisting of ground anthracene powder, tetracene, and graphite powder. Their proposed mechanism involved electronic excitation at the contacts between the graphite particles and the anthracene molecules.
The first Polymer LED to be created was by Roger Partridge at the National Physical Laboratory in the United Kingdom. It used a film of polyvinylcarbazole up to 2.2 micrometers thick located between two charge-injecting electrodes. The light generated was readily visible in normal lighting conditions though the polymer used had 2 limitations; low conductivity and the difficulty of injecting electrons. Later development of conjugated polymers would allow others to largely eliminate these problems. His contribution has often been overlooked due to the secrecy NPL imposed on the project. When it was patented in 1974 it was given a deliberately obscure "catch all" name while the government's Department for Industry tried and failed to find industrial collaborators to fund further development.
Practical OLEDs
Chemists Ching Wan Tang and Steven Van Slyke at Eastman Kodak built the first practical OLED device in 1987. This device used a two-layer structure with separate hole transporting and electron transporting layers such that recombination and light emission occurred in the middle of the organic layer; this resulted in a reduction in operating voltage and improvements in efficiency.Research into polymer electroluminescence culminated in 1990, with J. H. Burroughes at the Cavendish Laboratory at Cambridge University, UK, reporting a high-efficiency green light-emitting polymer-based device using 100nm thick films of poly. Moving from molecular to macromolecular materials solved the problems previously encountered with the long-term stability of the organic films and enabled high-quality films to be easily made. Subsequent research developed multilayer polymers and the new field of plastic electronics and OLED research and device production grew rapidly. White OLEDs, pioneered by J. Kido et al. at Yamagata University, Japan in 1995, achieved the commercialization of OLED-backlit displays and lighting.
In 1999, Kodak and Sanyo had entered into a partnership to jointly research, develop, and produce OLED displays. They announced the world's first 2.4-inch active-matrix, full-color OLED display in September the same year. In September 2002, they presented a prototype of 15-inch HDTV format display based on white OLEDs with color filters at the CEATEC Japan.
Manufacturing of small molecule OLEDs was started in 1997 by Pioneer Corporation, followed by TDK in 2001 and Samsung-NEC Mobile Display, which later became one of the world's largest OLED display manufacturers - Samsung Display, in 2002.
The Sony XEL-1, released in 2007, was the first OLED television. Universal Display Corporation, one of the OLED materials companies, holds a number of patents concerning the commercialization of OLEDs that are used by major OLED manufacturers around the world.
On 5 December 2017, JOLED, the successor of Sony and Panasonic's printable OLED business units, began the world's first commercial shipment of inkjet-printed OLED panels.
Working principle
A typical OLED is composed of a layer of organic materials situated between two electrodes, the anode and cathode, all deposited on a substrate. The organic molecules are electrically conductive as a result of delocalization of pi electrons caused by conjugation over part or all of the molecule. These materials have conductivity levels ranging from insulators to conductors, and are therefore considered organic semiconductors. The highest occupied and lowest unoccupied molecular orbitals of organic semiconductors are analogous to the valence and conduction bands of inorganic semiconductors.Originally, the most basic polymer OLEDs consisted of a single organic layer. One example was the first light-emitting device synthesised by J. H. Burroughes et al., which involved a single layer of poly. However multilayer OLEDs can be fabricated with two or more layers in order to improve device efficiency. As well as conductive properties, different materials may be chosen to aid charge injection at electrodes by providing a more gradual electronic profile, or block a charge from reaching the opposite electrode and being wasted. Many modern OLEDs incorporate a simple bilayer structure, consisting of a conductive layer and an emissive layer. Developments in OLED architecture in 2011 improved quantum efficiency by using a graded heterojunction. In the graded heterojunction architecture, the composition of hole and electron-transport materials varies continuously within the emissive layer with a dopant emitter. The graded heterojunction architecture combines the benefits of both conventional architectures by improving charge injection while simultaneously balancing charge transport within the emissive region.
During operation, a voltage is applied across the OLED such that the anode is positive with respect to the cathode. Anodes are picked based upon the quality of their optical transparency, electrical conductivity, and chemical stability. A current of electrons flows through the device from cathode to anode, as electrons are injected into the LUMO of the organic layer at the cathode and withdrawn from the HOMO at the anode. This latter process may also be described as the injection of electron holes into the HOMO. Electrostatic forces bring the electrons and the holes towards each other and they recombine forming an exciton, a bound state of the electron and hole. This happens closer to the electron-transport layer part of the emissive layer, because in organic semiconductors holes are generally more mobile than electrons. The decay of this excited state results in a relaxation of the energy levels of the electron, accompanied by emission of radiation whose frequency is in the visible region. The frequency of this radiation depends on the band gap of the material, in this case the difference in energy between the HOMO and LUMO.
As electrons and holes are fermions with half integer spin, an exciton may either be in a singlet state or a triplet state depending on how the spins of the electron and hole have been combined. Statistically three triplet excitons will be formed for each singlet exciton. Decay from triplet states is spin forbidden, increasing the timescale of the transition and limiting the internal efficiency of fluorescent OLED emissive layers and devices. Phosphorescent organic light-emitting diodes or emissive layers make use of spin–orbit interactions to facilitate intersystem crossing between singlet and triplet states, thus obtaining emission from both singlet and triplet states and improving the internal efficiency.
Indium tin oxide is commonly used as the anode material. It is transparent to visible light and has a high work function which promotes injection of holes into the HOMO level of the organic layer. A second conductive layer is typically added, which may consist of PEDOT:PSS, as the HOMO level of this material generally lies between the work function of ITO and the HOMO of other commonly used polymers, reducing the energy barriers for hole injection. Metals such as barium and calcium are often used for the cathode as they have low work functions which promote injection of electrons into the LUMO of the organic layer. Such metals are reactive, so they require a capping layer of aluminium to avoid degradation. Two secondary benefits of the aluminum capping layer include robustness to electrical contacts and the back reflection of emitted light out to the transparent ITO layer.
Experimental research has proven that the properties of the anode, specifically the anode/hole transport layer interface topography plays a major role in the efficiency, performance, and lifetime of organic light-emitting diodes. Imperfections in the surface of the anode decrease anode-organic film interface adhesion, increase electrical resistance, and allow for more frequent formation of non-emissive dark spots in the OLED material adversely affecting lifetime. Mechanisms to decrease anode roughness for ITO/glass substrates include the use of thin films and self-assembled monolayers. Also, alternative substrates and anode materials are being considered to increase OLED performance and lifetime. Possible examples include single crystal sapphire substrates treated with gold film anodes yielding lower work functions, operating voltages, electrical resistance values, and increasing lifetime of OLEDs.
Single carrier devices are typically used to study the kinetics and charge transport mechanisms of an organic material and can be useful when trying to study energy transfer processes. As current through the device is composed of only one type of charge carrier, either electrons or holes, recombination does not occur and no light is emitted. For example, electron only devices can be obtained by replacing ITO with a lower work function metal which increases the energy barrier of hole injection. Similarly, hole only devices can be made by using a cathode made solely of aluminium, resulting in an energy barrier too large for efficient electron injection.