Organic Light Emitting Diodes (OLEDs)

By: William Klema, Nathan Schares, Weston Smith EE 332 with Dr. Dalal

ABSTRACT With a growing demand for energy today, it is becoming more important to produce light efficiently. In recent years LED technology has been advancing rapidly to make LED (and OLED) technology an efficient source of light. In addition to efficient ambient lighting, OLEDs have given rise to a new era of display devices that are efficient, thin, flexible, and transparent. This document focuses on the physical structure, operation, manufacturing, uses, and future applications of OLEDs.

I. INTRODUCTION One of the most rapidly evolving semiconductor technologies today is the field of Light Emitting Diodes (LEDs). In the past, LEDs were commonly used as indicators for DC electric circuits but are rapidly evolving to provide large amounts of visible light for a wide range of lighting products. One of the first commercial lighting applications appeared in New Hampshire on May 17, 1996 when traffic signals utilizing LED technology were installed [1]. Since then, LEDs have proven to be a viable, long lasting, and energy efficient technology, rapidly moving into a number of other industries including automotive, home & entertainment lighting, and many others. A. Brief History of LEDs The LED dates back to 1955 when Rubin Braunstein first reported a semiconductor device would emit infrared light from a Gallium Arsenide (GaAs) junction [2]. His discoveries lead scientists Robert Biard and Gary Pittman to continue developing the infrared LED, which received a US Patent in 1961. The following year, Dr. Nick Holonyak received a patent for his Gallium Arsenic Phosphor (GaAsP) LED which was the first LED that emitted visible light (red in color). Visible light LEDs made their way into consumer electronics less than a decade later, commonly in the form of seven segment displays, some of which were used in watches (Fig. 1), VCRs, hand held calculators, and even early electronic games [3].

Fig.1, right: Pulsar’s first Digital Watch with LED technology which retailed for $2,100 in 1972 and was marketed as a “Time Computer”[4] LEDs have come a long way since their invention. They

LEDs are now produced with a wide variety of specifications including physical size, power requirements, packaging, and light output (wavelength and intensity). These wide ranges of specifications have led LEDs to finding a home in many electronics that we use every day. One of the most advanced uses of LEDs has been the emerging development of Organic Light Emitting Diodes (OLEDs). OLEDs operate similarly to traditional LEDs, with the exception that their emissive layer is composed of organic material. This process allows for OLEDs to be manufactured on a much smaller scale than traditional LEDs, which has led to the production of high resolution displays (and even flexible displays) that utilize this technology. B. Efficiency of LEDs Light Emitting Diodes have several advantages over conventional (incandescent) lighting. The most prominent advantage is power consumption. Traditional incandescent bulbs have a luminous efficiency of approximately 10-17 lumens per Watt (lm/W) compared to compact fluorescents 40-70 lm/W [5] and finally CREE’s X-Lamp white LEDs which have an efficiency of 132 lm/W [6]. Efficiency will only continue to climb, while costs decrease, as predicted by Haitz’s Law. In addition to being efficient, LEDs are durable. The average service life of LEDs are measured in years instead of months, and LEDs retain a much higher percentage of rated light intensity over a longer period of time when compared to incandescent bulbs. With all the benefits of LED technology, it is no wonder that many companies are integrating LED technology into their products. LED technology has become one of the fastest growing sectors in the semiconductor industry.

II. PHYSICS OF OLED OPERATION To understand the physics of an OLED, one must first understand the physics of a standard LED and how an electron moving into a lower energy state emits light. A. LED Basic Structure Like many semiconductor devices, LEDs operate using a PN junction. Often times a PN junction is created between two different materials, which is called a hetero-junction. Shown below in Fig. 2 & Fig.3, are diagrams of both the physical layout and the energy band diagram of a basic PN junction. In this diagram we can see the P-doped region as well as the N-doped region. When dealing with OLEDs, the P-doped region is referred to as the Hole Transport Layer (HTL) and the N-doped region is referred to as the the Electron Transport Layer (ETL).

Fig. 2. Cross-Section of Junction [7]

Fig. 3. Energy band Diagrams for Equilibrium and forward bias [8] B. Understanding Light Emission Basic structure is critical for semiconductor operation. Under forward bias, the barrier height of the conduction and valence bands are minimized, allowing current due to electrons or holes to flow across the junction. LEDs use cleverly designed junctions that take advantage of electron-hole recombination. The main idea behind light emission is to excite electrons using an external (forward) bias voltage and control the “jumping” of electrons from the conduction band to the lower energy state in the valence band (recombination). The loss of energy from “jumping” electrons is realized in the form of light energy (emitted photons) according to the equation E = hν where E is energy [eV], h is Planck’s constant [eV-sec] and ν is the frequency of light [sec-1]. Typically, the energy lost by an electron is equivalent to the energy band gap of the material being used. Fig. 4 illustrates the movement and recombination of electrons.

Fig. 4. Diagram of LED operation [9]

C. Wavelengths, Band Gaps and Materials

Fig. 5. Relative Intensity vs. Wavelength [10] Fig. 5 shows colors of light and their location in the visible spectrum. LEDs can emit light in and beyond the visible color spectrum. The wavelength of light emitted by the LED corresponds to the band gap of the electroluminescent material used inside of the LED.

D. OLED Operation and materials Organic LEDs operate using the same principles of traditional LEDs but use organic materials (small molecule materials) or electroluminescent polymers as the light emitting layer of the diode. Using these materials gives manufacturers the ability to create very small (and inherently thin) LEDs that can be used for high resolution displays. This technology is proving viable largely due to advances in manufacturing technology, overall power efficiency, and the stunningly small size. Organic materials used to construct OLEDs are pi-bonded materials. A pi-bonded material is a material composed of either single and double bonds, or single and triple bonds, which alternate throughout the material [11]. The energy difference between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) corresponds to the energy an electron will lose as it moves from the higher energy state to the lower energy state, and based on Plancks equation, the wavelength of light [11]. The energy difference between the HOMO and the LUMO is equivalent to the energy band gap of conventional LEDs. 1) Small molecule based OLEDs: The first successful OLED was developed by Tang and VanSlyke in 1987. It was considered successful because it emitted a high-intensity light with the application of a relatively low DC voltage (~7V) [14]. Tang and VanSlyke were the first to use a double layered organic thin film, with each layer only capable of monopolar transport, and they accredit their OLED success to this double layered design [14]. The double layers were composed of organic materials known as small molecule materials, which are by definition not polymers [11]. Tang and VanSlyke used aromatic diamine for the HTL and 8-hydroxyquinoline aluminum (Alq3) for the ETL. The anode was made of a transparent material, indium tin oxide

(ITO), and the cathode was constructed from a magnesium silver alloy (MgxAg1-x). Tang and VanSlyke concluded that the emitted light corresponded to the band gap of Alq3 (550nm or green light), and they found that the majority of recombination was taking place inside of the ETL, which confirmed that the ETL/HTL interface adequately controls the recombination process [14]. 2) Polymer based OLEDs: In contrast to small molecule technology, OLEDs can also be constructed using polymers. The first group to achieve successful electroluminescence from a polymer was Friend and coworkers in 1990 [15]. They used a synthesized solution of poly(pphenylene vinylene) (PPV) as the electroluminescence source and found that it emitted a greenyellow light easily visible in regular laboratory lighting [15]. Polymer OLEDs show greater potential over small molecule OLEDs because of lower fabrication costs and the robust, flexible structures they form; however, scientists are struggling to obtain polymers that are durable and have the ability to release a specific wavelength of light [15]. 3) Materials used in OLEDs: Researchers have synthesized many materials for use as the electroluminescent source inside an OLED. Each material has its own unique energy gap between its HOMO and LUMO (corresponding to the light it emits), and its own electron/hole mobilities. The properties of some of the most widely used materials are shown in Tbl. 1.

HOMO (eV)

LUMO (eV)

Energy gap (eV)

µh (cm2/V-s)

Triphenyl diamine (TPD)

5.6

2.5

3.1

1-2 x 10-3

Copper phthlocyanine (CuPc)

4.8

3.1

1.7

1 x 10-3

Poly(p-phenylene vinylene) (PPV)*

5.1

2.5

2.6

5 x 10-7

8-hydroxyquinoline aluminum (Alq3)

5.9

3.2

2.7

2 x 10-8

4,4’-bis(2,2’-diphenylvinyl) -1,1’-biphenyl (DPVBi)

5.9

2.8

3.1

ETLs

HTLs

Material

µn (cm2/V-s)

1.4 x 10-6

Tbl. 1. Widely used organic materials [11] HOMO and LUMO are relative to the vacuum level Electron and hole mobilities at fields of 105-106 V/cm The mobilities of electrons and holes in organic materials, typically 10-7-10-3 cm2/V-s, are much lower than the mobilities in inorganic materials. This is due to the disorder inside of the organic materials [11]. Organic materials can be doped with dyes to change the wavelengths of light emitted. The dye must have a lesser energy gap between its HOMO and LUMO than the base material. Alq3 is often used as the base material due to its large energy gap. Alone, Alq3 emits green light, but when a dye is added it can emit yellow or red light, depending on the energy gap of the dye [11]. Indium tin oxide (ITO) is used widely as the anode because it is transparent and has a high work function, allowing it to easily transmit holes into the HTL [11]. Polyaniline (PANI), a flexible plastic, is used widely as the anode in flexible OLED applications [11]. Variations of a magnesium silver alloy (MgxAg1-x) are often used as the cathode due to its low work function, which enables a smooth transport of electrons into the ETL [11].

4) White OLEDs: An enormous demand for white OLEDs is present our current society because we are accustomed to white ambient lighting. One method of creating a white OLED is to fabricate a multi-layer device that will emit multiple wavelengths of light. The combination of these wavelengths can be carefully selected to span the entire visible spectrum resulting in the generation of white light. An example of such a device was provided by J. Shinar [11] and is shown in Fig. 6.

Fig. 6. Layout of a white OLED (not to scale) The device above will emit light corresponding to the energy gaps of TPD (violet), Alq3 (green), and Nile Red-doped Alq3 (red), resulting in white light [11]. Another method of fabricating a white OLED is to use dye-doped polymers such as poly(N-vinyl carbazole) (PVK) or poly(methyl methacrylate) (PMMA). These polymers are weakly emissive, but they can be doped with a variety of lower-gap dyes, which can be selected to emit light throughout the visible spectrum, resulting in white light [11].

III. PHYSICAL PROPERTIES OF THE OLED A. Basic Structure of OLEDs Fig. 6 shows the basic structural layout of an OLED. The OLED is made up of two semiconducting layers: an Electron Transport Layer (ETL), and a Hole Transport Layer (HTL). The ETL is synonymous with n-type material in an LED, and the HTL corresponds to the p-type material in an LED [12]. The cathode, which connects to the negative terminal of the power supply, is connected to the ETL and is generally a metal or metal alloy with a low work function (~3 to 4 eV) to allow for efficient injection of electrons into the OLED. The anode, which connects to the positive terminal of the power supply, is connected to the HTL and is generally a metal with a high work function (~5 eV) to allow for a smooth transfer of holes into the OLED [12]. For the emitted light to be visible, at least one half of the OLED must be transparent. In most cases, both the anode and substrate are chosen to be transparent [11].

Fig. 6. Basic Structure of an OLED Multiple layers of organic films are often used inside of the ETL and HTL to increase the performance of the OLED [11].

B. Efficiency One of the biggest hurdles in the development of OLED technology is achieving a high level of light-emitting efficiency. The efficiency of an OLED is measured as the ratio between the photons emitted per charge carriers injected. The biggest hurdle in the battle for efficiency is controlling where and when electron-hole pairs (EHPs) recombine to emit light inside of the OLED. If the recombination occurs outside of the desired area, unintended wavelengths of light may be emitted. If the recombination does not happen at all, ohmic heating takes place, greatly reducing the lifespan of the OLED [11]. This problem is solved by selecting organic materials capable of only monopolar transport, assuring that carrier recombination takes place in or around the organic hetero-junction [14]. Other researchers have extended this idea and incorporated more than two layers of organic materials to further control the flow of electrons, holes, and the emitting properties of the device [11]. C. Degradation Mechanisms Another large problem OLED technology faces is the degradation of the organic materials used in the devices. The first OLEDs that Tang and VanSlyke built in 1987 lost about 30% of electroluminescence emission in the first few hours [14]. Dark spots are the most prominent form of degradation in small molecule and polymer based OLEDs. Degradation occurs on the metal/organic interface and is caused by ohmic heating due to electrons or holes passing through the OLED and not recombining [11]. By effectively controlling the recombination of the EHPs, this problem can be eliminated.

D. Fabrication The fabrication of an OLED can be separated into two main categories: thermal vacuum evaporation and wet-coating. Thermal vacuum evaporation is primarily used to construct small molecule OLEDs, while wet-coating is the preferred fabrication method of polymer based OLEDs. 1) Thermal vacuum evaporation: Thermal vacuum evaporation is capable of accurately depositing very thin films of materials onto substrates. This is done by heating the deposited material in a vacuum chamber until it evaporates. The vapors of the material settle on the substrate (also inside of the vacuum chamber) resulting in a thin film of material forming on the substrate. A basic thermal vacuum evaporation system is shown in Fig. 7.

Fig. 7. Basic thermal vacuum evaporation system The advantages of this method are: 1) multiple layers of different materials can easily be deposited and 2) the thickness of each layer can be controlled with extreme accuracy (~10 A) [4]. This procedure can be used to deposit almost any material except polymers [11]. Patterns in

depositions can be controlled with masks [12]. The equipment necessary for such a method of deposition is extremely expensive [12]. 2) Spin-coating: Fig. 8 shows the most basic wet-coating procedure, spin-coating. It involves applying the polymer onto the substrate (in liquid form) and spinning the substrate at a high speed, resulting in an evenly coated substrate. This method, by far, is the cheapest for fabricating OLEDs; however, it neither accurately controls the thickness of the applied material, nor does it allow for a localized application of the material [11].

Fig. 8. Spin-coating 3) Ink-jet printing: Another method of wet-coating is inkjet printing. In this method, polymers can be deposited directly onto the substrate using a specialized inkjet printer. This allows for the organic light-emitting layers to be manufactured with extreme accuracy. Because of its ability to arrange different colored OLEDs in an array pattern to form pixels, inkjet printing is the preferred method in the development of full-color OLED displays. Cambridge Display Technologies, Seiko-Epson, and Philips are currently utilizing this method in the development of OLED display technology [11].

IV. STATUS OF OLED TECHNOLOGY A. Use in Visual Displays With OLEDs being capable of producing very small, intense sources of light, they have a current primary application in the visual display market. OLED displays are projected to overtake the now cheap and readily available Liquid Crystal Display (LCD). Not unlike LCD displays, OLED displays are designed as an active-matrix or a passive-matrix. 1) Active- matrix OLED (AMOLED): In an active-matrix design, pixels are formed by a

full cathode layer, a thin film transistor (TFT), and an anode layer. Each type of organic material between the anode and cathode produces a specific color. The current flowing through each pixel is controlled with a MOSFET transistor (Fig. 9) and is proportional its brightness [17]. A voltage is applied to a capacitor connected to the gate of the transistor on each pixel. Since there is minimal current leakage through the gate of the transistor, each pixel is able to retain a value for its brightness until it is refreshed [17]. Active-matrix designs are ideal because they are capable of high refresh-rates and consume minimal power [16].

Fig. 9. Design of a AMOLED [17]

2) Passive-matrix OLED (PMOLED): PMOLEDs are similar to AMOLEDs except they are composed of strips of cathode, anode, and organic layers. The anode and cathode strips are arranged perpendicular, forming a grid, as shown in Fig. 10. External circuitry applies current to a specific row and column, activating the LED light at the intersection [16]. PMOLEDs are easy to make, but consume more power than AMOLEDs and are often found in small devices such as cell phone displays [16].

Fig. 10. Design of a PMOLED [16]

3) Market presence: Currently OLED displays hold a relatively small portion of the

display market mainly due to the fact that: OLED technology is new, OLED manufacturing processes are relatively expensive, and LCD displays have become cheap and abundant. OLED displays are currently found in small-sized devices such as the “Kodak LS633 EasyShare” digital camera, which features a 2.2” OLED display, as shown in Fig.11 [18]. Small devices are able to utilize PMOLED displays, as they are cheap and satisfy the requirements of simple displays; however, it will be sometime before consumers see larger AMOLED televisions (42” – 60”) in retail stores.

Large OLED displays, such as televisions, will be of AMOLED design and take advantage of fast refresh-rates and minimal energy consumption. Currently, several leaders in the television market such as Sony, Samsung, and Panasonic have unveiled beautiful HD AMOLED prototype TVs, Fig. 12.

Fig. 11. Canon LS633 [18]

Fig. 12. Samsung 40” AMOLED TV prototype [19]

Large AMOLED TVs are projected to be on shelves by the end of 2011, according to Panasonic, “who just invested $930.4 million into an OLED panel mass production facility in Himeji, Japan” [19]. The plant is expected to start operation in 2010. With an investment that large, it is no secret that OLED technology will have a dominating presence in the future display market. 4) OLED advantages: With companies investing close to a billion dollars in OLED technology, there must be several advantages over current display technologies such as plasma and LCD. The two main advantages of OLED displays are: a. Each OLED pixel produces its own light, eliminating the need for a backlight. In an LCD display, there is one back-light usually consisting of high-voltage fluorescent bulbs. The LCD essentially allows light through certain pixels, and blocks others. This approach produces poor contrast ratios, because light often shines through “blocked” pixels, and LCDs also use a considerable amount of energy to power the high-voltage backlight. OLED displays only activate

the pixels needed for the picture, producing much better contrast ratios and consuming much less power than LCD displays. b. OLEDs displays are much more flexible, lighter, and thinner because they use thin organic layers to produce light, allowing OLEDs to use a thin, flexible substrates instead of glass [16]. Making the substrates transparent, in addition to thin and flexible, opens a gateway into a whole new world of display possibilities.

V. FUTURE APPLICATIONS OF OLED TECHNOLOGY A. Large Scale Displays

Imagine walking into a class room and seeing screen only a few millimeters thick displaying high definition video without the need of a LCD projector: the screen is the projector itself! This vision may become a reality in a few short years. Thin, flexible, and often transparent substrates will allow OLED displays to be lightweight, efficient, and adaptable. One possible application could be an interactive whiteboard, where instructors can combine slide shows with traditional teaching methods by writing directly on an OLED display, shown in Fig. 13. Software would track virtual marker movement, allowing instructors to archive lectures and board-work.

A+B=C

OLED Display Fig. 13. Combining a white-board and OLED display

B. Ambient Lighting OLEDs can be used for more than just displays; they can also serve as an efficient source of ambient light. Using thin arrays of white OLEDs, manufacturers can produce whole sheets light instead of individual bulbs. White OLED array applications are endless. Imagine replacing traditional drop-ceiling tiles with efficient OLED tiles. OLED panels surpass current energy savings technologies by offering an even distribution of light compared to traditional LEDs, and eliminating the need for harmful mercury vapor found in fluorescent bulbs [20]. Manufacturers such as Lumiotec have already released OLED prototypes, shown in Fig. 14.

Fig. 14. Stylish Lumiotec OLED prototype panels [20] C. Optical chemical and bio sensors One interesting application of OLED, researched by Jon Hiram at Iowa State University, is using OLEDs, a photoluminescent sensor, and a photodector, to monitor the level of a desired gas. The goal of the device is to be “fully integrated, inert sensing, self-calibrated, miniature, flexible, and inexpensive to the point of being disposable” [12]. Demand for this device is quite high. According to H.H. Weetall, “The chemical industry is looking for real-time methods for monitoring and quantitating [the] differential analysis of gas mixtures” [12]. He goes on to say that chemical sensor technology is lagging behind the rest of the chemical industry, and there is a need to replace expensive electrochemical sensors [12]. The OLED optical chemical sensor, shown in Fig. 15, utilizes efficient and inexpensive OLEDs, which are integrated into the sensing device. The light from the OLED passes through the gas or liquid to be measured, and is read by a photodector.

Photodector

PL

Gas flow or liquid cell Photoluminescent sensor EL Glass Substrate Organic EL material Electrode

Fig. 15. Structure of integrated OLED sensor [12]. D. Foldable OLEDs Flexible substrates in OLEDs give rise to the idea of foldable newspaper-style OLED arrays. Imagine carrying an OLED newspaper that updates in real-time with the latest news [16]. Another interesting idea is the integration of flexible OLEDs into clothing. OLEDs could improve the safety of road workers and firefighters by making their clothing more visible, as shown in Fig.16.

Fig. 16. Illuminated safety clothing [21]

VI. CONCLUSION With the overwhelming benefits of OLEDs and the fact that companies are investing nearly $1 billion, it is clear that OLED technology will be the foundation of lighting and displays for years to come. Applications of OLEDs are endless and can be attributed mostly to their flexible substrates. OLED displays and lighting are energy efficient, making them a viable solution to our energy problem; however, it will still be some time before OLED production costs are completive with current technologies.

REFERENCES [1]

“Sending a bright signal”, Concord Monitor pg B-6, 18 May 1996 10 November 2009.

[2]

“The Quartz Watch [Inventors]” Smithsonian.org 10 November 2009.

[3]

Dr. Nick Holonyak Jr., Consumer Electronics Association 10 November 2009

[4]

“Cool Watches” Smithsonian.org 11 November 2009.

[5]

“Lighting Efficiency Comparison” Madison Gas & Electric 10 November 2009.

[6]

CREE X-Lamp XP-G Datasheet 10 November 2009.

[7]

Image From: 12 November 2009.

[8]

Image From: E.F. Schubert 12 November 2009.

[9]

Image From: 15 November 2009.

[10]

Image & Data From: oksolar.com 15 November 2009.

[11]

J. Shinar, Organic light-emitting devices: a survey, New York: AIP Press/Springer, 2004.

[12]

J. H. Friedl, “Preparation, characterization, and application of organic light emitting diodes,” M.S. thesis, Iowa State University, Ames, IA, 1999.

[14]

C. W. Tang and S. A. VanSlyke, “Organic electroluminescent diodes,” Applied Physics Letters, Vol. 51, Issue 12, pp.913-915, Sept. 1987.

[15]

D. D. C. Bradley, A. R. Brown, P. L. Burns, J. H. Burroughes, R. H. Friend, A. B. Holmes, K. Mackay, and R. N. Marks, “Light-emitting diodes based on conjugated polymers,” Nature, Vol. 347, pp.539-541, Oct. 1990.

[16]

Freudenrich, Ph.D., Craig. "How OLEDs Work." HowStuffWorks.com. 24 March 2005. . 9 November 2009.

[17]

Antoniadis, Homer, Ph.D. "Overview of OLED Display Technology." Osram Optical Semiconductors. .

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“Kodak LS633 First with OLED Display” Digital Photography Review. 2 March 2003. . 11 November 2009.

[19]

“Matsushita/Panasonic joins the OLED TV race” Gizmag. 30 July 2008. < http://www.gizmag.com/matsushita-joins-oled-tv-race/9722/>. 12 November 2009.

[20]

“OLED Lighting” OLED-Info. 14 November 2008. < http://www.oled-info.com/oled-light>. 15 November 2009.

[21]

“I Saw the Light – and it Bends” GE Reports. 30 June 2009. < http://www.gereports.com/ges-oled-research>. 15 November 2009.

Organic Light Emitting Diodes (OLEDs)

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