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Principles and Applications of Organic Light Emitting Diodes (OLEDs)

Principles and Applications of Organic Light Emitting Diodes (OLEDs)

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Principles and Applications of Organic Light Emitting Diodes (OLEDs)

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May 15, 2017


Principles and Applications of Organic Light Emitting Diodes (OLEDs)explores the ways in which the development of organic semiconductor materials is opening up new applications in electronic and optoelectronic luminescent devices.

The book begins by covering the principles of luminescence and the luminescent properties of organic semiconductors. It then covers the development of luminescent materials for OLEDs, discussing the advantages and disadvantages of organic versus inorganic luminescent materials. The fabrication and characterization of OLEDs is also covered in detail, including information on, and comparisons of, vacuum deposition and solution techniques.

Finally, applications of OLEDs are explored, including OLEDs in solid-state lighting, colored lighting, displays and potential future applications, such as ultra-thin and flexible technologies.

This book is an excellent resource both for experts and newcomers to the field of organic optoelectronics and OLEDs. It is ideal for scientists working on optical devices, lighting, display and imaging technologies, and for all those engaged in research in photonics, luminescence and optical materials.

  • Provides a one-stop guide to OLED technology for the benefit of newcomers to the field of organic optoelectronics
  • Comprehensively covers the luminescent properties of organic semiconductors and their development into OLED materials
  • Offers practical information on OLED fabrication and their applications in solid-state lighting and displays, making this essential reading for optoelectronics engineers and materials scientists
Lançado em:
May 15, 2017

Sobre o autor

Dr. N. Thejo Kalyani is working as an Assistant Professor in the Department of Applied Physics, Laxminarayan Institute of Technology, Nagpur, India. She obtained her Master’s degree in Physics from Sri Venkateswara University, Tirupati, India. She completed her doctoral research from R.T.M. Nagpur University, Nagpur, India in 2010 on the topic entitled “Development of Red Organic Light Emitting Diode (OLED)”. Her research interests include the synthesis, characterization of various organic complexes and fabrication of OLED devices and displays by vacuum deposition and solution techniques. She has published 42 peer-reviewed research papers in national and international journals of repute besides 16 other publications including book chapters and 28 papers in conference proceedings. She also co-authored an Elsevier book on “Principles and applications of organic light emitting diodes”. She is a reviewer for many national and international journals. She has authored 10 Textbooks for B.E/ B.Tech /B.Sc in highly reputed International and National Publishers. She is associated with various professional bodies such as Material Research Society of India, Luminescence Society of India.

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Principles and Applications of Organic Light Emitting Diodes (OLEDs) - N. Thejo Kalyani


Chapter 1


Basic Principles and Applications


Exploration of lighting technology is based on a solid understanding of the fundamental principles of luminescence. Luminescence refers to cool emission, caused by the movement of electrons within a substance from high energetic state to less energetic state, thereby giving off light at normal or cool temperatures without generating heat. The practical value of luminescent materials lies in their capacity to transform invisible forms of energy into visible light. Luminescence efficiency depends on the degree of transformation of excitation energy into light energy. There are relatively few materials that have sufficient luminescence efficiency to be of practical value. This chapter explores the classification of luminescence based on time lag, source of excitation, mechanism of light emission, terminology, and applications of luminescence.


Luminescence; fluorescence; phosphorescence; antenna effect; screening effect; rare earths

1.1 Introduction

Since time immemorial, light emissions from glowworms, sea creatures, and the extravagant light shows of the aurora borealis have been fascinating, and a great deal of work has been done to comprehend their origins. Until the advent of quantum mechanics, the basic origins of these emissions could not be adequately understood. Later, after numerous resourceful attempts to determine the origin behind these emissions, it was finally concluded that they are due to the phenomena of luminescence, which involves the absorption of suitable energy and subsequent emission of light as ultraviolet (UV), visible light, or infrared (IR) radiation from materials. Over time, major breakthroughs in luminescence studies made this field of research a major focus of innovation.

1.2 Light

Light has fascinated mankind since ancient times through its diverse shades and colors as it plays a vital role in almost all spheres of modern life. Various natural wonders such as the shades of sunrises and sunsets, rainbows, the blues of ocean and sky, etc., involve light. But what is light? In simple terms, it is a physical quantity that is emitted by a luminous body and when incident on the eye causes the sensation of sight through nerves. It constitutes a tiny proportion of the whole electromagnetic spectrum that is visible to the human eyes. Though our capabilities for perception of light are highly elevated, only a very narrow range of the electromagnetic spectrum, which extends from the deepest violet (400 nm) to the deepest red (750 nm), can be seen by us. According to the wavelength and frequency, the color of light also changes and hence a spectrum of VIBGYOR can be observed. In VIBGYOR, red occupies more space and hence reaches our eyes first. Red, green, and blue (RGB) occupies two-thirds of the spectrum and a specific combination thereof creates white light. The visible (VIS) spectrum and its wavelength range and bandwidth of the different colors of the VIS spectrum are shown in Fig. 1.1 and Table 1.1, respectively.

Figure 1.1 Visible spectrum [1].

Table 1.1

Wavelength range and band width of different colors of the visible spectrum [1]

The emission of wavelengths corresponding to the visible region requires a minimum excitation energy ranging between 1.8 and 3.1 eV as calculated by Einstein’s law. This law states that the excitation energy (E) is equal to the ratio of Planck’s constant (h) times the velocity of light (c) in vacuum to its wavelength (λ), which is given by

1.3 Mechanism of Light Emission

Light is a form of energy and hence another form of energy is needed to create light. This is practically possible by two phenomenon, namely incandescence and luminescence. Light is electromagnetic radiation generated by changes in vibration of electrically charged particles from heated molecules or by the downward transition of electrons in atoms. The first phenomenon is known as incandescence while the latter is known in luminescence.

1.3.1 Incandescence

If a material is heated to a high enough temperature, it starts glowing. This process in which light is emitted from heat energy is known as incandescence. When atoms are heated, they release some of their thermal vibrations as electromagnetic radiation in the form of incandescent light. This is the most common type of light obtained from the sun, stars, a burning piece of coal, and a piece of iron heated to very high temperature. The sun provides almost all of the heat, light, and other forms of energy that are necessary for life on our planet by the process of incandescence. Stars twinkle red if their temperature is low and glow blue if the temperature is high because different temperatures result in different colors. Similarly, a piece of iron appears dark at room temperature and when heated, it appears faint crimson at 500°C, then turns red, orange, gradually yellow at 800°C, and finally emits white light above 1000°C due to incandescence. This phenomenon of light emission is well explained by Planck’s black-body emission theory. Incandescence Sources

Among many sources of light available, the most common light sources are thermal sources, which emit light in the form of hot emission, e.g., when the tungsten filament or ordinary incandescent lightbulb is heated, it glows brightly white hot due to incandescence, hence the popularity of incandescent lamps. These incandescent sources consist of a filament made of tungsten, a special metal that can stay at a high temperature for more than 100 hours without burning (oxidizing). The sun and the filament of an electric bulb are shown in Fig. 1.2A. When electrical current runs through a thin wire, the resistance creates heat. When the wire reaches a high temperature, the atoms in the material absorb energy and the electrons are excited to the higher energy states. After their lifetime, they return to the lower energy state along with the emission of light and heat. In these lamps only 15% of light is emitted in the visible range and the rest is released in the form of heat [2] as shown in Fig. 1.2B. According to the inverse square law, the intensity of light per unit area varies in inverse proportion to the square of the distance between the source and targeted area. The distance is measured to the first luminating surface—the filament of a clear bulb, or the glass envelope of a frosted bulb. If I denotes the intensity of light per unit area and d is the distance between the source and targeted area, then the flux density E is given by the following relation:

Figure 1.2 Demonstration of incandescence in (A) (i) sun and (ii) filament of an electric bulb and (B) intensity versus wavelength of thermal radiation at different temperatures.

For example, if an incandescent lamp emits 40 lm/m² at a distance of 0.5 m, it can emit only 10 lm/m² if the distance is increased to 1 m as shown in Fig. 1.3.

Figure 1.3 Incandescent lamp—demonstration of inverse square law [3].

As the intensity of light drastically varies with distance they are not effective sources of lighting. Filament break is the usual end of the lamp life and hence they are least expensive to purchase and most expensive to operate. Light-conversion efficiency can be represented mathematically as:

Thus the efficiency of an incandescent bulb is only 15% and the remaining energy is lost in the form of heat.

1.3.2 Luminescence

German physicist and science historian Eilhard Wiedemann was the first to introduce the term luminescence, which comes from the Latin root Lumin, meaning light [4]. In general, luminescence is the study of the laws of absorption and emission of radiation by matter [5]. Luminescence is cool emission caused by the movement of electrons within a substance from more energetic states to less energetic states and hence it is a process of giving off light at normal or cool temperatures without generating heat. This can be caused by absorption of photons, chemical or biochemical reactions, activity of subatomic particles, radiation, or stress on a crystal. The wavelength of light emitted is characteristic of luminescent substance and not of the incident radiation [6,7]. The law of luminescence states that the wavelength of emitted radiation is always greater than the exciting radiation (λemi > λexc). The materials emitting luminescence are called luminophors or phosphors [8]. Fig. 1.4 shows the luminescence process.

Figure 1.4 Schematic diagram of the luminescence process: (A) electron in lowest energy state, (B) excited state, and (C) light emission.

Luminescence is an interdisciplinary subject as it is applicable to various fields such as physics, chemistry, biological science, medical science, forensic science, geology, material science, engineering technology, etc. Current research is characterized by strong interaction among other branches of solid state and between different areas of luminescence using inorganic and organic materials. Luminescence in Transition Metal Ions

Transition metals are those elements in which atoms have a partially filled d subshell or an incomplete d subshell that can give rise to cations [9,10]. f-Block lanthanide and actinide series are also considered as transition metals, and are generally called inner-transition metals. Color in transition-series metal compounds is generally due to electronic transitions of two major types, namely (1) charge transfer transitions, where an electron can jump from a ligand orbital to metal orbital, giving rise to a ligand-to-metal charge-transfer (LMCT) transition; and (2) d–d transitions, where an electron jumps from one d-orbital to another d-orbital. Such transitions are more likely to occur when the metal is in a low-oxidation state. Vibrant colors can be obtained from dichromate and permanganate ions and aqueous solutions of transition metal ions [Co (NO3)2 (red); K2Cr2O7 (orange)]. Luminescence in Rare Earth Metal Complexes

Luminescence is the distinguishing and appealing feature of lanthanide trivalent ions. Rare earth metals are a family of 17 elements with atomic numbers 21, 39, and 57–71. Of these, the element with atomic no. 57, Lanthanum (La), has no free electron in the 4f shell, while the element with atomic no. 71, Lutetium (Lu), has a completely filled 4f shell with 14 electrons. One peculiar characteristic of all 13 elements among the rare earths, starting from Cerium (Ce) to Ytterbium (Yb), is that the 4f shell is incompletely filled, but is completely screened by the outer 5s and 5p subshells, which are completely filled. The optical and electromagnetic properties of these 13 rare-earth elements are essentially due to the screening of this incompletely filled 4f shell. Luminescence in tripositive rare earth ions arises mainly due to energy-level transition within the 4f shell, which is generally forbidden by quantum mechanical spin and parity prohibition rules. Efficient luminescence can still occur in these ions under conditions where such ions do not occupy a position having a center of symmetry in a crystalline lattice. Some of the tripositive ions such as Europium (Eu³+), Terbium (Tb³+), and Dysprosium (Dy³+) are good luminescent emitters, a factor depending on the number of electrons in its 4f shell. The ions, which are inert to luminescent emission, are those of Yb, La, Ga, and Lu. Table 1.2 describes and classifies rare earth metals.

Table 1.2

Descriptive classification of rare earth metals [11]

Origin of Luminescence in Lanthanides: Screening Effect

Lanthanides from Ce³+ to Lu³+ have 1 to 14 4f electrons added to their inner-shell configuration, which is equivalent to Xe. Ions with no 4f electrons, i.e., Sc³+, Y³+, La³+, and Lu³+, have no electronic energy levels that can induce excitation and luminescence processes in or near the visible region. In contrast, the ions from Ce³+ to Yb³+, which have partially filled 4f orbitals, have energy levels characteristic of each ion and show a variety of luminescence properties around the visible region. Many of these ions can be used as luminescent ions in phosphors, mostly by replacing Y³+, Gd³+, La³+, and Lu³+ in various compounds.

The luminescence from the lanthanide ions is the result of competition between radiative and nonradiative pathways in the relaxation of an electronically excited species. By the selection rule ΔJ = 0, ±1 (ΔJ = 0 is forbidden), hypothetically in lanthanide ions only magnetic dipole transitions are permissible [12]. In the coordinating sphere of lanthanide, electric-dipole transitions are also preferential as the ligand field mixes slightly odd parity configurations into the [Xe] 4fn 5d° configuration. As coordinating chromophores absorb energy, most of the lines of absorption and emission come out due to electric-dipole transition. Both magnetic-dipole and electric-dipole transitions of lanthanide ions are quite weak as compared to fully allowed transitions in organic chromophores separately. The excited state of lanthanides is not solely relaxed by a radiative process but also by nonradiative processes. The emissive properties of lanthanides can be enhanced by increasing the excited state population and minimizing nonradiative pathways. In the case of lanthanides, the emission is due to transitions inside the 4f shell, i.e., these transitions are intraconfigurational f–f transitions. The deep-lying partially filled 4f shell, which is not completely filled with electrons, is well shielded by those outer 5s²5p⁶ shells (except in La³+ and Lu³+), which gives rise to the number of discrete energy levels and the ligands in the first and second coordination spheres perturbing the electronic configurations of the trivalent lanthanide ions only to a very limited extent.

This shielding, also known as the screening effect, is responsible for the specific properties of lanthanide luminescence, specifically for the narrow-band emission and for the long lifetimes of the excited states. Most of the lanthanide ions show luminescence in the visible region of the optical spectrum [13,14]. The energy-level diagram for the Ln(III) ions showing the main emissive levels and the possible transitions to the ground-state levels is well illustrated in Fig. 1.5 through the Dieke diagram.

Figure 1.5 Dieke diagram: Energy-level diagram for the Ln(III) ions showing the main emissive levels and the possible transitions to the ground state levels [15].

The Antenna Effect: Sensitized Emission

In the early 1990s, Lehn [16] coined the term antenna to denote the absorption, energy transfer, and emission sequence involving distinct absorbing (the ligand) and emitting (the lanthanide ion) components in luminescent lanthanide complexes that work as light-conversion molecular devices (LMCDs). The antenna effect in lanthanides and organic chelate is well illustrated in Fig. 1.6. The introduction of an antenna in lanthanide complexes provides an alternate pathway for energy transfer and enriches the lanthanide-emitting levels, which then relax to ground state by emitting light [17–19]. For an effective sensitization process in sensitizer–functionalized–lanthanide complexes for various applications generally the chromophore should fulfill some requirements: (1) The antenna chromophore should possess a high molar extinction coefficient to obtain high photoluminescence quantum yield in the process of absorption-energy transfer-emission. (2) The antenna chromophore should match the triplet state energy levels for effective energy transfer to the lanthanide luminescent states.

Figure 1.6 Illustration of antenna effect.

If the energy transfer between donor and acceptor is too large, it may lead to slower energy-transfer rates, whereas a thermally activated back energy transfer can occur in a small energy gap. (3) The antenna chromophore should be in close proximity to the lanthanides ion for effective energy transfer. (4) The intersystem crossing yield of the antenna chromophore should be high. (5) To get rid of the quenching problem by water or solvent molecules, the antenna chromophore should saturate the inner coordination sphere of lanthanide metal ions with a coordination number of at least 8.

Ligand and Lanthanide Ion Excitation: Jablonski Diagram

The ligand-enhanced lanthanide luminescence mechanism is basically a three-step process: (1) The ligand absorbs the excitation light; (2) the absorbed energy is transferred to the lanthanide ions; and (3) finally, the ions emit light. In addition to the previously introduced central ion energy levels, there are several ligand energy levels involved in the process [20]. These steps related to lanthanide luminescence are well illustrated by the Jablonski diagram. The energy levels in this diagram are arranged vertically by energy and grouped horizontally by spin multiplicity as depicted in Fig. 1.7.

Figure 1.7 Illustration of lanthanide luminescence by the Jablonski diagram [21], where IC, internal conversion; ISC, intersystem crossing; ILCT, intraligand charge-transfer; LMCT, ligand-to-metal charge transfer; IET, intramolecular energy transfer; RET, rare earth transition.

In the ligand–lanthanide complex the absorption of a photon is a very fast process (~10−15 s) that occurs from the energetically lowest ground state, since in a nonexcited molecule electrons tend to occupy these energetically lowest lying levels. Most lanthanide complexes are excited at the near-UV range (the wavelengths rarely exceeding 350 nm). From the original excited singlet energy level of the ligand, the electrons may decay nonradiatively by means of internal conversion (within 10−12 s) to some excited vibrational level, or to the lowest excited electronic level. The sensitization process may involve several ligand singlet and triplet states and also intraligand charge-transfer (ILCT) states. Traditionally the energy flow is considered to depart from the ligand singlet state to the ligand triplet state by intersystem crossing, and from the (lowest) ligand triplet state through intramolecular energy transfer to the excited energy levels of the central ion [22–24]. In some cases, the singlet state may directly transfer energy to the central ion. This is, however, not common, since the singlet state is short lived and thus the process is not efficient [25].

There are two main mechanisms for the intramolecular energy transfer from the triplet state of the ligand to the central ion: (1) the Dexter (electron exchange) mechanism and (2) the Förster (dipole–dipole) mechanism. The Dexter mechanism involves a mutual electronic exchange between the ligand and the central ion [26] requiring physical contact between the two components. On the other hand, in the Förster mechanism, the triplet-state transition dipole moment associates with the dipole moment of the 4f orbitals. For this reason, the Förster mechanism does not require physical contact between the components and therefore functions at longer distances compared to the Dexter mechanism [27,28]. In addition to these main mechanisms, other mechanisms for exciting the central ion, e.g., the metal-to-ligand charge transfer (MLCT) from chromophore containing d-transition metal ions [29] and the ligand-to-metal charge transfer (LMCT) [30], are also possible. Schematic diagrams of the Förster and Dexter mechanisms are shown in Fig. 1.8.

Figure 1.8 Schematics of the Förster and Dexter mechanisms [31].

The charge-transfer transitions are allowed, but they require high energies, which are most prominent with Sm³+, Eu³+, and Yb³+, as these are the most easily reduced ions. When utilizing the LMCT states to transfer energy to the excited 4f states of the lanthanide ion, the energy of the LMCT state should be high enough compared to the emitting energy level of the ion to minimize quenching of the luminescence. In addition to the f–f transitions and charge-transfer transitions, lanthanide ions also display a third type of electronic transitions: the f–d transitions, i.e., the promotion of a 4f electrons into the 5d subshell. The f–d transitions are allowed, are broader than f–f transitions, and (contradictory to f–f transitions) their spectral position largely depends on the ligand field. The physical, chemical, thermal, and optical properties of lanthanides are given in Table 1.3.

Table 1.3

Physical, chemical, thermal, and optical properties of lanthanides [32–40]

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