Patent Publication Number: US-8994059-B2

Title: Organic light emitting diodes and methods of manufacturing the same

Description:
CROSS-REFERENCE TO RELATED APPLICATION 
     This application is a divisional of application Ser. No. 13/494,532, filed on Jun. 12, 2012. Further, this application claims the benefit of priority of Korean Patent Application No. 10-2011-0090366, filed on Sep. 6, 2011. The disclosure of these prior U.S. and Korean applications are incorporated herein by reference. 
    
    
     BACKGROUND 
     The inventive concept relates to light emitting devices and methods of manufacturing the same and, more particularly, to organic light emitting diodes and methods of manufacturing the same. 
     Recently, a display industry may have been developed for satisfying demands of small size, lightness, thinness, and high resolution of display devices. For example, organic light emitting diodes (OLEDs) are attractive in next generation-flat panel display devices and next generation-illumination market. The organic light emitting diodes may have excellent display characteristics such as wide view angle, fast response speed, thin thickness, low manufacturing costs, and high contrast. 
     The organic light emitting diode may correspond to a self-emitting device which electrically excites an organic light emitting material to emit light. The organic light emitting diode may include a substrate, a first electrode, a second electrode, and an organic light emitting layer formed between the first and second electrodes. The organic light emitting layer may generate light by recombination of holes and electrons supplied from the first and second electrodes. The organic light emitting diode may output various colors of light according to kinds of materials constituting the organic light emitting layer. However, a conventional organic light emitting diode may have a scattering layer between the organic light emitting layer and the first electrode or between the first electrode and the substrate. A guided mode loss may occur in the organic light emitting diode having the scattering layer, such that light extraction efficiency of the organic light emitting diode may decrease. 
     SUMMARY 
     Embodiments of the inventive concept may provide organic light emitting diodes capable of increasing or maximize light extraction efficiency and methods of manufacturing the same. 
     Embodiments of the inventive concept may also provide organic light emitting diodes capable of increasing or maximize productivity and methods of manufacturing the same. 
     In one aspect, an organic light emitting diode may include: a substrate; a first electrode layer and a second electrode layer formed on the substrate; an organic light emitting layer between the first electrode layer and the second electrode layer, the organic light emitting layer generating light; and a scattering layer between the first electrode layer and the substrate or between the first electrode layer and the organic light emitting layer, the scattering layer scattering the light. 
     In some embodiments, the scattering layer may include fine patterns. 
     In other embodiments, the substrate may include a recess formed at a top surface thereof. Here, the fine patterns may be disposed along an inner surface of the recess. 
     In still other embodiments, the recess may have a micro lens-shape. 
     In yet other embodiments, the fine patterns may include polymer. 
     In yet still other embodiments, the polymer may include at least one of polystyrene, polybutadiene, polybutylacrylate, polyisoprene, polyhexylacrylate, polyisobutylene, polybutylmethacrylate, polyethylethylene, polyvinylpyridine, and polyethyleneoxide. 
     In yet still other embodiments, each of the fine patterns may have a width within a range of about 100 nm to about 700 nm. 
     In yet still other embodiments, the fine patterns may correspond to concave-convex parts formed at a top surface of the substrate. 
     In yet still other embodiments, the scattering layer may further include a planarization layer covering the fine patterns. 
     In yet still other embodiments, the planarization layer may include at least one of inorganic materials of TiO 2 , ZrO 2 , ZnS, TiO 2 -SiO 2 , SnO 2 , and In 2 O 3 , polymers of polyvinyl phenolic resin, epoxy resin, polyimide resin, polystyrene resin, polycarbonate resin, polyethylene resin, polymethylmethacrylate (PMMA) resin, and polypropylene resin, and any combination thereof. 
     In another aspect, a method of manufacturing an organic light emitting diode may include: preparing a substrate; forming a scattering layer on the substrate; forming a first electrode layer on the scattering layer; forming an organic light emitting layer on the first electrode layer; and forming a second electrode layer on the organic light emitting layer. 
     In some embodiments, forming the scattering layer may include: forming fine patterns on the substrate; and forming a planarization layer covering the fine patterns. 
     In other embodiments, forming the fine patterns may include: forming a polymer layer on the substrate; rearranging the polymer layer into first polymer blocks and second polymer blocks by a phase separation method; and removing the first polymer blocks or the second polymer blocks. 
     In still other embodiments, the polymer layer may include block copolymer formed by a spin coating method. 
     In yet other embodiments, the block copolymer may include at least one of polystyrene-polymethylmethacrylate copolymer, polybutadiene-polybutylmethacrylate copolymer, polybutadiene-polydimethylsiloxane copolymer, polybutadiene-polymethylmethacrylate copolymer, polybutadiene-polyvinylpyridine copolymer, polybutylacrylate-polymethylmethacrylate, polybutylacrylate-polyvinylpyridine, polyisoprene-polyvinylpyridine, polyisoprene-polymethylmethacrylate, polyhexylacrylate-polyvinylpyridine, polyisobutylene-polybutylmethacrylate, polyisobutylene-polymethylmethacrylate, polyisobutylene-polybutylmethacrylate, polyisobutylene-polydimethylsiloxane, polybutylmethacrylate-polybutylacrylate, polyethylethylene-polymethylmethacrylate, polystyrene-polybutylmethacrylate, polystyrene-polybutadiene, polystyrene-polyisoprene, polystyrene-polydimethylsiloxane, polystyrene-polyvinylpyridine, polyethylethylene-polyvinylpyridine, polyethylene-polyvinylpyridine, polyvinylpyridine-polymethylmethacrylate, polyethyleneoxide-polyisoprene, polyethyleneoxide-polybutadiene, polyethyleneoxide-polystyrene, polyethyleneoxide-polymethylmethacrylate, polyethyleneoxide-polydimethylsiloxane, and polystyrene-polyethyleneoxide. 
     In yet still other embodiments, the block copolymer may be rearranged into the first polymer blocks and the second polymer blocks by a thermal treatment. The phase separation method may include the thermal treatment. 
     In yet still other embodiments, the first polymer blocks or the second polymer blocks may be removed by a cleaning solution after the first and second polymer blocks are exposed by ultraviolet rays. 
     In yet still other embodiments, forming the fine patterns may include: etching the substrate exposed from the first polymer blocks or the second polymer blocks which remain on the substrate. 
     In yet still other embodiments, the planarization layer may include at least one of inorganic materials of TiO 2 , ZrO 2 , ZnS, TiO 2 -SiO 2 , SnO 2 , and In 2 O 3 , polymers of polyvinyl phenolic resin, epoxy resin, polyimide resin, polystyrene resin, polycarbonate resin, polyethylene resin, polymethylmethacrylate (PMMA) resin, and polypropylene resin, and any combination thereof. The planarization layer may be formed by a spin coating method. 
     In yet still other embodiments, preparing the substrate may include: forming recesses at a top surface of the substrate. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       The inventive concept will become more apparent in view of the attached drawings and accompanying detailed description. 
         FIG. 1  is a cross-sectional view illustrating an organic light emitting diode according to a first embodiment of the inventive concept; 
         FIGS. 2A to 2F  are cross-sectional views illustrating a method of manufacturing an organic light emitting diode according to a first embodiment of the inventive concept; 
         FIG. 3  is a cross-sectional view illustrating an organic light emitting diode according to a second embodiment of the inventive concept; 
         FIGS. 4A to 4G  are cross-sectional views illustrating a method of manufacturing an organic light emitting diode according to a second embodiment of the inventive concept; 
         FIG. 5  is a cross-sectional view illustrating an organic light emitting diode according to a third embodiment of the inventive concept; 
         FIGS. 6A to 6H  are cross-sectional views illustrating a method of manufacturing an organic light emitting diode according to a third embodiment of the inventive concept; 
         FIG. 7  is a cross-sectional view illustrating an organic light emitting diode according to a fourth embodiment of the inventive concept; and 
         FIGS. 8A to 8E  are cross-sectional views illustrating a method of manufacturing an organic light emitting diode according to a fourth embodiment of the inventive concept. 
     
    
    
     DETAILED DESCRIPTION OF THE EMBODIMENTS 
     The inventive concept will now be described more fully hereinafter with reference to the accompanying drawings, in which exemplary embodiments of the inventive concept are shown. The advantages and features of the inventive concept and methods of achieving them will be apparent from the following exemplary embodiments that will be described in more detail with reference to the accompanying drawings. It should be noted, however, that the inventive concept is not limited to the following exemplary embodiments, and may be implemented in various forms. Accordingly, the exemplary embodiments are provided only to disclose the inventive concept and let those skilled in the art know the category of the inventive concept. In the drawings, embodiments of the inventive concept are not limited to the specific examples provided herein and are exaggerated for clarity. 
     The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention. As used herein, the singular terms “a,” “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. It will be understood that when an element is referred to as being “connected” or “coupled” to another element, it may be directly connected or coupled to the other element or intervening elements may be present. 
     Similarly, it will be understood that when an element such as a layer, region or substrate is referred to as being “on” another element, it can be directly on the other element or intervening elements may be present. In contrast, the term “directly” means that there are no intervening elements. It will be further understood that the terms “comprises”, “comprising,”, “includes” and/or “including”, when used herein, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. 
     Additionally, the embodiment in the detailed description will be described with sectional views as ideal exemplary views of the inventive concept. Accordingly, shapes of the exemplary views may be modified according to manufacturing techniques and/or allowable errors. Therefore, the embodiments of the inventive concept are not limited to the specific shape illustrated in the exemplary views, but may include other shapes that may be created according to manufacturing processes. Areas exemplified in the drawings have general properties, and are used to illustrate specific shapes of elements. Thus, this should not be construed as limited to the scope of the inventive concept. 
     It will be also understood that although the terms first, second, third etc. may be used herein to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another element. Thus, a first element in some embodiments could be termed a second element in other embodiments without departing from the teachings of the present invention. Exemplary embodiments of aspects of the present inventive concept explained and illustrated herein include their complementary counterparts. The same reference numerals or the same reference designators denote the same elements throughout the specification. 
     Moreover, exemplary embodiments are described herein with reference to cross-sectional illustrations and/or plane illustrations that are idealized exemplary illustrations. Accordingly, variations from the shapes of the illustrations as a result, for example, of manufacturing techniques and/or tolerances, are to be expected. Thus, exemplary embodiments should not be construed as limited to the shapes of regions illustrated herein but are to include deviations in shapes that result, for example, from manufacturing. For example, an etching region illustrated as a rectangle will, typically, have rounded or curved features. Thus, the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the actual shape of a region of a device and are not intended to limit the scope of example embodiments. 
       FIG. 1  is a cross-sectional view illustrating an organic light emitting diode according to a first embodiment of the inventive concept. 
     Referring to  FIG. 1 , an organic light emitting diode according to a first embodiment may include a fine patterns  20  formed between a substrate  10  and a first electrode layer  40 . The substrate  10  may be formed of a transparent material such as a glass or a plastic. Each of the fine patterns  20  may have a size of a visible light wavelength band (e.g., about 10 2  nm). The fine patterns  20  may be disposed on the substrate  10  randomly (e.g., non-periodicity). The fine patterns  20  may include at least one polymer selected from a group consisting of polystyrene, polybutadiene, polybutylacrylate, polyisoprene, polyhexylacrylate, polyisobutylene, polybutylmethacrylate, polyethylethylene, polyvinylpyridine, and polyethyleneoxide. The fine patterns  20  may be disposed in a planarization layer  30  and increase scattering of light. The planarization layer  30  covers the fine patterns  20 . For example, the planarization layer  30  may include a transparent material including at least one of silicon oxide (e.g., spin-on-glass (SOG)), titanium oxide (TiO 2 ), and tantalum oxide (Ta 2 O 5 ). The planarization layer  30  may have a refractive index higher than those of an organic light emitting layer  50  and the first electrode layer  40 . The planarization layer  30  may increase light extraction efficiency in the organic light emitting layer  50  and the first electrode layer  40 . The planarization layer  30  and the fine patterns  20  may constitute a scattering layer. 
     Thus, the organic light emitting diode according to the first embodiment of the inventive concept may increase or maximize the light extraction efficiency by light scattering. 
     The first electrode layer  40  may be formed of a conductive material having a transparency. For example, the first electrode layer  40  may include at least one of transparent conductive oxides (TCOs). In more detail, the first electrode layer  40  may include indium tin oxide (ITO) or indium zinc oxide (IZO). Additionally, the first electrode layer  40  may include graphene having a thickness within a range of about 1 nm to about 10 nm. 
     The organic light emitting layer  50  may include an organic light emitting material. For example, the organic light emitting layer  50  include at least one of polyfluorene derivatives, (poly)paraphenylenevinylene derivatives, polyphenylene derivatives, polyvinylcarbazole derivatives, polythiophene derivatives, anthracene derivatives, butadiene derivatives, tetracene derivatives, distyrylarylene derivatives, benzazole derivatives, and carbazole. Additionally, the organic light emitting layer  50  may include an organic light emitting material including dopants. For example, the dopants may include at least one of xanthene, perylene, cumarine, rhodamine, rubrene, dicyanomethylenepyran, thiopyran, (thia)pyrilium, periflanthene derivatives, indenoperylene derivatives, carbostyryl, nile red, and quinacridone. 
     The organic light emitting layer  50  may have a single-layered structure, or a multi-layered structure including an assistant layer. In other words, the organic light emitting layer  50  may include at least one layer including at least one of the organic light emitting materials described above, and the assistant layer increasing light emitting efficiency of the organic light emitting layer  50 . The assistant layer may include at least one of a hole injecting layer, a hole transfer layer, an electron transfer layer, and an electron injecting layer. The organic light emitting layer  50  may generate light by recombination of holes and/or electrons supplied from the first electrode layer  40  and/or a second electrode layer  60 . 
     The second electrode layer  60  may include a conductive material. For example, the second electrode layer  60  may include at least one of aluminum (Al), silver (Ag), magnesium (Mg), and molybdenum (Mo). Additionally, the second electrode layer  60  may include a transparent conductive material. The second electrode layer  60  may be applied with a voltage from an external system, so that the second electrode layer  60  may apply electrons into the organic light emitting layer  50 . The second electrode layer  60  may transmit the light generated from the organic light emitting layer  50  or reflect the light toward the first electrode layer  40 . Even though not shown in the drawings, a passivation layer may be disposed on the second electrode layer  60 . 
     A method of manufacturing the organic light emitting diode described above will be described hereinafter. 
       FIGS. 2A to 2F  are cross-sectional views illustrating a method of manufacturing an organic light emitting diode according to a first embodiment of the inventive concept. 
     Referring to  FIG. 2A , a polymer layer  24  is formed on a substrate  10 . The polymer layer  24  may be formed on the substrate  10  by a spin coating method. The polymer layer  24  may include a block copolymer consisting of a first polymer block  26  and a second polymer block  28 . The first polymer block  26  and the second polymer block  28  may be covalently bonded to each other in a volume ratio of 1:1. The block copolymer may be formed of linear type or branched type polymer having a molecular weight within a range of about 3,000 g/mol to 2,000,000 g/mol. For example, the block copolymer may include at least one of polystyrene-polymethylmethacrylate copolymer, polybutadiene-polybutylmethacrylate copolymer, polybutadiene-polydimethylsiloxane copolymer, polybutadiene-polymethylmethacrylate copolymer, polybutadiene-polyvinylpyridine copolymer, polybutylacrylate-polymethylmethacrylate, polybutylacrylate-polyvinylpyridine, polyisoprene-polyvinylpyridine, polyisoprene-polymethylmethacrylate, polyhexylacrylate-polyvinylpyridine, polyisobutylene-polybutylmethacrylate, polyisobutylene-polymethylmethacrylate, polyisobutylene-polybutylmethacrylate, polyisobutylene-polydimethylsiloxane, polybutylmethacrylate-polybutylacrylate, polyethylethylene-polymethylmethacrylate, polystyrene-polybutylmethacrylate, polystyrene-polybutadiene, polystyrene-polyisoprene, polystyrene-polydimethylsiloxane, polystyrene-polyvinylpyridine, polyethylethylene-polyvinylpyridine, polyethylene-polyvinylpyridine, polyvinylpyridine-polymethylmethacrylate, polyethyleneoxide-polyisoprene, polyethyleneoxide-polybutadiene, polyethyleneoxide-polystyrene, polyethyleneoxide-polymethylmethacrylate, polyethyleneoxide-polydimethylsiloxane, and polystyrene-polyethyleneoxide. However, the inventive concept is not limited thereto. In other embodiments, various other block polymers may be used as the polymer layer  24 . The polymer layer  24  may include a first homo polymer and a second homo polymer constituted by the same repeating units as the first polymer block  26  and the second polymer block  28 , respectively. 
     The polymer layer  24  may be rearranged into the first polymer blocks  26  and the second polymer blocks  28  phase-separated from each other by a phase separation method. Polarities of the first polymer block  26  and the second polymer block  28  may be different from each other according to repeating unit structures constituting the first and second polymer blocks  26  and  28 . The polymer layer  24  may be divided into the first polymer blocks  24  and the second polymer blocks  26  to be rearranged at a temperature higher than a glass transition temperature (Tg) of the block copolymer. The phase separation method of the polymer layer  24  may include a self-assembled method using a thermal treatment. For example, when the polymer layer  24  of polystyrene-polymethylmethacrylate copolymer is thermally treated at about 200 degrees Celsius under argon (Ar) atmosphere, the polymer layer  24  may be divided into the first polymer blocks  26  of polystyrene and the second polymer blocks  28  of polymethylmethacrylate to be rearranged. 
     Referring to  FIG. 2B , one of the first polymer block  26  and the second polymer block  28  may be removed to form fine patterns  20  consisting of the other of the first and second polymer blocks  26  an  28  which remains. The fine patterns  20  may expose portions of the substrate  10 . One of the first and second polymer blocks  26  and  28  may be stripped by a cleaning solution after exposure of ultraviolet rays or may be selectively removed by a solvent. For example, polymethylmethacrylate may be exposed by the ultraviolet rays so as to be phase-separated from polystyrene. The polymethylmethacrylate may be dissolved in toluene or acetic acid. An ultrasonic wave may accelerate the removal of the polymethylmethacrylate. The first polymer block  26  or the second polymer block  28  remaining on the substrate  10  may be thermally treated. As illustrated in  FIG. 2B , for example, the first polymer blocks  26  may be removed to form the fine patterns  20  formed of the second polymer blocks  28 . However, the inventive concept is not limited thereto. In other embodiments, the second polymer blocks  28  may be removed to form the fine patterns  20  formed of the first polymer blocks  26 . In this case, it is possible to identically obtain effects according to the inventive concept. Thus, it is possible to increase or maximize productivity by the method of manufacturing the organic light emitting diode according to the first embodiment of the inventive concept. 
     Referring to  FIGS. 1 and 2C , a planarization layer  30  is formed to cover the fine patterns  20 . The planarization layer  30  may include at least one of inorganic materials (e.g., TiO 2 , ZrO 2 , ZnS, TiO 2 -SiO 2 , SnO 2 , and In 2 O 3 ), polymers (e.g., polyvinyl phenolic resin, epoxy resin, polyimide resin, polystyrene resin, polycarbonate resin, polyethylene resin, polymethylmethacrylate (PMMA) resin, and polypropylene resin), and any combination thereof. The planarization layer  30  may be formed by a spin coating method. 
     Referring to  FIGS. 2D to 2F , a first electrode layer  40 , an organic light emitting layer  50 , and a second electrode layer  60  sequentially stacked on the planarization layer  30 . The first electrode layer  40  and the second electrode layer  60  may be formed by a sputtering method. The first electrode layer  40  may include a transparent conductive material such as indium tin oxide (ITO) or indium zinc oxide (IZO). The second electrode layer  60  may include at least one of gold, silver, tungsten, copper, and aluminum. The organic light emitting layer  50  may be formed by a spin coating method. The organic light emitting layer  50  may include at least one of polyfluorene derivatives, (poly)paraphenylenevinylene derivatives, polyphenylene derivatives, polyvinylcarbazole derivatives, polythiophene derivatives, anthracene derivatives, butadiene derivatives, tetracene derivatives, distyrylarylene derivatives, benzazole derivatives, and carbazole. 
     Thus, the method of manufacturing the organic light emitting diode according to the first embodiment may increase or maximize productivity. 
       FIG. 3  is a cross-sectional view illustrating an organic light emitting diode according to a second embodiment of the inventive concept. 
     Referring to  FIG. 3 , an organic light emitting diode according to a second embodiment of the inventive concept may include recesses  12  formed in an upper portion of a substrate  10  and fine patterns  20  formed along the recesses  12 . The recesses  12  may have micro lens-shapes. The recess  12  may have a width and a depth greater than a width of the fine pattern  20 . For example, the recess  12  may have the width within a range of about 1 μm to about 1 mm and the depth within a range of about 1 μm to about 1 mm. The fine pattern  20  may have the width within a range of about 100 nm to about 700 nm. The fine patterns  20  may be disposed along inner surfaces of the recesses  12 . The fine patterns  20  may include at least one polymer selected from a group consisting of polystyrene, polybutadiene, polybutylacrylate, polyisoprene, polyhexylacrylate, polyisobutylene, polybutylmethacrylate, polyethylethylene, polyvinylpyridine, and polyethyleneoxide. The recesses  12  and the fine patterns  20  may scatter light proceeding from the organic light emitting layer  50  toward the substrate  10 . 
     Thus, the organic light emitting diode according to the second embodiment of the inventive concept may increase or maximize the light extraction efficiency by light scattering. 
       FIGS. 4A to 4G  are cross-sectional views illustrating a method of manufacturing an organic light emitting diode according to a second embodiment of the inventive concept. 
     Referring to  FIG. 4A , recesses  12  are formed at an upper surface of a substrate  10 . The recesses  12  may be formed by a photolithography process and an etching process. Photoresist patterns may be formed on the substrate  10  by the photolithography process. The etching process may etch a surface of the substrate which is exposed from the photoresist patterns, such that the recesses  12  may be formed in the upper portion of the substrate  10 . The etching process may include a wet etching process isotropically etching the surface of the substrate  10 . The photoresist patterns may be removed. 
     Referring to  FIG. 4B , a polymer layer  24  is formed on the recesses  12  of the substrate  10 . The polymer layer  24  may include the block copolymer described in the first embodiment. The polymer layer  24  may be divided into first polymer blocks  26  and second polymer blocks  28  to be rearranged at a temperature higher than a glass transition temperature (Tg) of the block copolymer. 
     Referring to  FIG. 4C , one of the first polymer block  26  and the second polymer block  28  in the polymer layer  24  may be removed to form fine patterns  20  consisting of the other of the first and second polymer blocks  26  and  28  which remains, on the recesses  12 . The one of the first and second polymer blocks  26  and  28  may be selectively removed by ultraviolet rays or chemical reaction of a solvent. For example, if polystyrene and polymethylmethacrylate are exposed by the ultraviolet rays, the polymethylmethacrylate may selectively react to the ultraviolet rays. The polymethylmethacrylate reacting to the ultraviolet rays may be removed by a development solution. Alternatively, the polystyrene may be thermally treated and then be formed into the fine patterns  20  remaining on the substrate  10 . The fine patterns  20  may be easily formed from the block copolymer without a photolithography process causing high manufacturing cost. Thus, the method of manufacturing the organic light emitting diode according to the second embodiment of the inventive concept may increase or maximize productivity. 
     Referring to  FIG. 4D , a planarization layer  30  is formed on the recesses  12  and the fine patterns  20 . The planarization layer  30  may include at least one of inorganic materials (e.g., TiO 2 , ZrO 2 , ZnS, TiO 2 -SiO 2 , SnO 2 , and In 2 O 3 ), polymers (e.g., polyvinyl phenolic resin, epoxy resin, polyimide resin, polystyrene resin, polycarbonate resin, polyethylene resin, polymethylmethacrylate (PMMA) resin, and polypropylene resin), and any combination thereof. The planarization layer  30  may be formed by a spin coating method. 
     Referring to  FIGS. 4E to 4G , a first electrode layer  40 , an organic light emitting layer  50 , and a second electrode layer  60  are sequentially formed on the planarization layer  30 . The first electrode layer  40  and the second electrode  60  may include metals formed by a sputtering method. The organic light emitting layer  50  may be formed by a spin coating method. The organic light emitting layer  50  may include at least one of polyfluorene derivatives, (poly)paraphenylenevinylene derivatives, polyphenylene derivatives, polyvinylcarbazole derivatives, polythiophene derivatives, anthracene derivatives, butadiene derivatives, tetracene derivatives, distyrylarylene derivatives, benzazole derivatives, and carbazole. 
     As a result, the method of manufacturing the organic light emitting diode according to the second embodiment may increase or maximize productivity. 
       FIG. 5  is a cross-sectional view illustrating an organic light emitting diode according to a third embodiment of the inventive concept. 
     Referring to  FIG. 5 , an organic light emitting diode according to a third embodiment of the inventive concept may include concave-convex parts  14  formed along a top surface of the substrate  10 . The concave-convex parts  14  may correspond to the fine patterns  20  in the first embodiment. Convex portions of the concave-convex parts  14  may be formed of the same material as the substrate  10 . The substrate  10  may include glass or plastic. Each of the convex portions of the concave-convex parts  14  may have a width within a range of about 100 nm to about 700 nm. In more detail, each of the convex portions of the concave-convex parts  14  may have the width within a range of about 400 nm to about 700 nm corresponding to a wavelength band of light. The concave-convex parts  14  may increase scattering of light transmitted into the first electrode layer  40  and the planarization layer  30  from the organic light emitting layer  50 . 
     Thus, the organic light emitting diode according to the third embodiment of the inventive concept may increase or maximize the light extraction efficiency by light scattering. 
       FIGS. 6A to 6H  are cross-sectional views illustrating a method of manufacturing an organic light emitting diode according to a third embodiment of the inventive concept. 
     Referring to  FIG. 6A , a polymer layer  24  is formed on a substrate  10 . The polymer layer  24  may include block copolymer formed by a spin coating method. The polymer layer  24  may be divided into first polymer blocks  26  and second polymer blocks  28  to be rearranged at a temperature higher than a glass transition temperature (Tg) of the block copolymer. 
     Referring to  FIG. 6B , one of the first polymer block  26  and the second polymer block  28  of the polymer layer  24  may be removed. The one of the first and second polymer blocks  26  and  28  may be removed by ultraviolet rays or a chemical reaction of a solvent. 
     Referring to  FIGS. 6C and 6D , a surface of the substrate  10 , which may be exposed from the other of the first and second polymer blocks  26  and  28  remaining on the substrate  10 , may be etched to form concave-convex part  14 . The substrate  10  may be etched by a dry etching method. The first polymer blocks  26  or the second polymer blocks  28  remaining on the substrate  10  may be used as etch masks during the etching process. The concave-convex parts  14  may correspond to fine patterns having widths within a range of about 400 nm to about 700 nm. 
     Referring to  FIG. 6E , a planarization layer  30  is formed on the concave-convex parts  14 . The planarization layer  30  may include at least one of inorganic materials (e.g., TiO 2 , ZrO 2 , ZnS, TiO 2 -SiO 2 , SnO 2 , and In 2 O 3 ), polymers (e.g., polyvinyl phenolic resin, epoxy resin, polyimide resin, polystyrene resin, polycarbonate resin, polyethylene resin, polymethylmethacrylate (PMMA) resin, and polypropylene resin), and any combination thereof. The planarization layer  30  may be formed by a spin coating method. 
     Referring to  FIGS. 6F to 6H , a first electrode layer  40 , an organic light emitting layer  50 , and a second electrode layer  60  are sequentially formed on the planarization layer  30 . The first electrode layer  40  and the second electrode  60  may include metals formed by a sputtering method. The organic light emitting layer  50  may be formed by a spin coating method. The organic light emitting layer  50  may include at least one of polyfluorene derivatives, (poly)paraphenylenevinylene derivatives, polyphenylene derivatives, polyvinylcarbazole derivatives, polythiophene derivatives, anthracene derivatives, butadiene derivatives, tetracene derivatives, distyrylarylene derivatives, benzazole derivatives, and carbazole. 
       FIG. 7  is a cross-sectional view illustrating an organic light emitting diode according to a fourth embodiment of the inventive concept. 
     Referring to  FIG. 7 , an organic light emitting diode according to a fourth embodiment of the inventive concept may include fine patterns  20  formed between a first electrode  40  and an organic light emitting layer  50 . The fine patterns  20  may include at least one polymer selected from a group consisting of polystyrene, polybutadiene, polybutylacrylate, polyisoprene, polyhexylacrylate, polyisobutylene, polybutylmethacrylate, polyethylethylene, polyvinylpyridine, and polyethyleneoxide. The light generated from the organic light emitting layer  50  may be scattered by the fine patterns  20 . 
     Thus, the organic light emitting diode according to the fourth embodiment of the inventive concept may increase or maximize the light extraction efficiency by light scattering. 
       FIGS. 8A to 8E  are cross-sectional views illustrating a method of manufacturing an organic light emitting diode according to a fourth embodiment of the inventive concept. 
     Referring to  FIG. 8A , a first electrode layer  40  is formed on a substrate  10 . The first electrode layer  40  may include a transparent conductive material such as indium tin oxide (ITO) or indium zinc oxide (IZO) formed by a sputtering method. 
     Referring to  FIG. 8B , a polymer layer  24  is formed on the first electrode layer  40 . The polymer layer  24  may include block copolymer formed by a spin coating method. The polymer layer  24  may be divided into first polymer blocks  26  and second polymer blocks  28  to be rearranged at a temperature higher than a glass transition temperature (Tg) of the block copolymer. 
     Referring to  FIG. 8C , one of the first polymer block  26  and the second polymer block  28  of the polymer layer  24  may be removed to form fine patterns  20  consisting the other thereof. The one of the first and second polymer blocks  26  and  28  may be removed by ultraviolet rays or a chemical reaction of a solvent. 
     Thus, the method of manufacturing the organic light emitting diode according to embodiments of the inventive concept may increase or maximize productivity. 
     Referring to  FIG. 8D , an organic light emitting layer  50  is formed on the fine patterns  20  and the first electrode layer  40 . The organic light emitting layer  50  may be formed by a spin coating method. The organic light emitting layer  50  may include at least one of polyfluorene derivatives, (poly)paraphenylenevinylene derivatives, polyphenylene derivatives, polyvinylcarbazole derivatives, polythiophene derivatives, anthracene derivatives, butadiene derivatives, tetracene derivatives, distyrylarylene derivatives, benzazole derivatives, and carbazole. 
     Referring to  FIG. 8E , a second electrode layer  60  is formed on the organic light emitting layer  50 . The second electrode layer  60  may include at least one of gold, silver, tungsten, copper, and aluminum. 
     As a result, the method of manufacturing the organic light emitting diode according to embodiments of the inventive concept may increase or maximize productivity. 
     According to embodiments of the inventive concept, the organic light emitting diode may include a scattering layer including fine patterns formed between the substrate and the first electrode layer or between the first electrode layer and the organic light emitting layer. Additionally, the scattering layer may be formed by a spin coating method. Thus, the organic light emitting diodes and the methods of manufacturing the same may increase or maximize light extraction efficiency by light scattering, and productivity. 
     While the inventive concept has been described with reference to example embodiments, it will be apparent to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the inventive concept. Therefore, it should be understood that the above embodiments are not limiting, but illustrative. Thus, the scope of the inventive concept is to be determined by the broadest permissible interpretation of the following claims and their equivalents, and shall not be restricted or limited by the foregoing description.