WO2015004889A1 - 有機el素子、および有機el表示パネル - Google Patents
有機el素子、および有機el表示パネル Download PDFInfo
- Publication number
- WO2015004889A1 WO2015004889A1 PCT/JP2014/003555 JP2014003555W WO2015004889A1 WO 2015004889 A1 WO2015004889 A1 WO 2015004889A1 JP 2014003555 W JP2014003555 W JP 2014003555W WO 2015004889 A1 WO2015004889 A1 WO 2015004889A1
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- WIPO (PCT)
- Prior art keywords
- organic
- light emitting
- doping concentration
- layer
- region
- Prior art date
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Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
- H10K50/165—Electron transporting layers comprising dopants
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
Definitions
- the present invention relates to the structure of an organic EL (Electro-Luminescence) element.
- the organic EL element is a current-driven light-emitting element, and has a structure in which an organic light-emitting layer that performs an electroluminescence phenomenon by recombination of carriers (holes and electrons) is interposed between an anode and a cathode electrode pair. .
- a sealing layer is provided above the cathode.
- Patent Document 1 discloses a technique for increasing the electron mobility of an electron transport layer and improving the light emission efficiency of an organic EL element by doping an electron transport layer with an n-type dopant containing an electron donating substance such as an alkali metal. It is disclosed.
- an undesired crack may occur in the sealing layer due to adhesion of minute foreign matters in the manufacturing process of the organic EL element.
- a crack may occur in the sealing layer.
- water or oxygen that has entered from the crack of the sealing layer reacts with the n-type dopant contained in the electron transport layer, and the doping concentration of the n-type dopant decreases.
- the light emission efficiency of the electron transport layer is lowered, and a defective light emitting region in which light emission luminance is reduced or non-light emission occurs.
- a defective light emitting region is easily noticeable to the user, and the commercial value as an organic EL element is greatly impaired.
- the present disclosure has been made in view of the above circumstances, and an object of the present disclosure is to provide an organic EL element in which even if an undesired defective light emitting region is generated, the defective light emitting region is hardly noticeable.
- an organic EL device includes an anode, a cathode, an organic light emitting layer provided between the anode and the cathode, the cathode, and the organic light emitting layer.
- the electron transport layer is provided with an electron transport layer, and the electron transport layer is doped with an n-type dopant containing an electron donating substance. It is characterized by being higher than the doping concentration at which the luminous efficiency is maximized.
- the doping concentration of the n-type dopant doped in the electron transport layer is higher than the doping concentration at which the emission efficiency of the organic light emitting layer is maximized, and therefore is adjacent to the defective light emitting region.
- the luminous efficiency is improved by decreasing the doping concentration of the n-type dopant. Since the luminous efficiency of the region adjacent to the defective light emitting region is improved and the light emission luminance is improved, the apparent size of the defective light emitting region is reduced, and the defective light emitting region is less noticeable to the user.
- FIG. 1 is a cross-sectional view illustrating a configuration of an organic EL element according to a first embodiment. It is a figure which shows the relationship between the doping density
- concentration of Ba of an organic EL element it is sectional drawing which shows the structure in the state which the crack produced in the sealing layer.
- FIG. 4 is an enlarged cross-sectional view of a portion surrounded by a broken line A in FIG. 3.
- Embodiment 1 It is a figure which shows the relationship between the position in the X direction of the organic EL element concerning Embodiment 1, the dope density
- (a) is Embodiment 1. It is a figure which shows the relationship between the doping density
- (b) shows the relationship between the position in the X direction of an organic EL element, and the doping concentration of an n-type dopant. It is a figure and (c) is a figure which shows the relationship between the position in the X direction of an organic EL element, and the luminous efficiency of an organic light emitting layer.
- (F) is a figure which shows the enlarged photograph of the foreign material which causes the defective light emission area
- An organic EL element which is one embodiment of the present disclosure includes an anode, a cathode, an organic light emitting layer provided between the anode and the cathode, and an electron provided between the cathode and the organic light emitting layer.
- An organic EL device having a transport layer, wherein the electron transport layer is doped with an n-type dopant containing an electron donating substance, and the doping concentration is a doping that maximizes the luminous efficiency of the organic light emitting layer. Higher than concentration.
- the light emitting efficiency of the organic light emitting layer is improved by decreasing the doping concentration of the n-type dopant in the electron transport layer. Since the light emission efficiency of the organic light emitting layer is improved and the light emission luminance is improved in a region adjacent to the defective light emitting region, the apparent size of the defective light emitting region is reduced and the defective light emitting region is less noticeable to the user.
- the organic EL element further includes a sealing layer provided on the side opposite to the electron transport layer with the cathode interposed therebetween, and the sealing layer is undesirable.
- the n-type dopant reacts with water or gas that has entered from the crack, the doping concentration gradually decreases toward the position closest to the crack in the electron transport layer.
- the region of the organic light emitting layer corresponding to the region where the doping concentration of the n-type dopant is gradually decreased there is a region where the light emission efficiency is maximized.
- the emission luminance of the organic light emitting layer is a region where the doping concentration of the n-type dopant in the electron transport layer gradually decreases toward the position closest to the crack. Will improve. Therefore, the apparent size of the defective light emitting area is reduced, and the defective light emitting area is less noticeable to the user.
- the n-type dopant is an alkali metal or an alkaline earth metal.
- the n-type dopant is barium.
- the barium dope concentration is higher than 15 [wt%].
- the luminous efficiency of the organic light emitting layer is maximized at a doping concentration of 15 [wt%]. Therefore, if the barium doping concentration in the electron transport layer is higher than 15 [wt%], the organic light emitting layer has a region where the barium doping concentration in the electron transport layer gradually decreases toward the position closest to the crack. There can be a region where the luminous efficiency is maximized.
- the doping concentration of barium is 25 [wt%] or more.
- the doping concentration of barium is 25 [wt%] or more, even if a foreign substance having a diameter that is difficult to remove is less than about 20 [ ⁇ m], the occurrence of a visible defective light emitting region can be suppressed. .
- the doping concentration of barium is 50 [wt%] or less.
- the doping concentration of barium is in the range of 50 [wt%] or less, the risk of leakage current occurring in the electron transport layer can be suppressed.
- an organic EL display panel which is one embodiment of the present disclosure includes the organic EL element described above.
- the light emitting efficiency of the organic light emitting layer is improved by decreasing the doping concentration of the n-type dopant in the electron transport layer in the region adjacent to the defective light emitting region. . Since the light emission efficiency of the organic light emitting layer is improved and the light emission luminance is improved in a region adjacent to the defective light emitting region, the apparent size of the defective light emitting region is reduced and the defective light emitting region is less noticeable to the user.
- FIG. 1 is a cross-sectional view illustrating the configuration of the organic EL element according to the first embodiment.
- the organic EL element 1 is a so-called top emission type organic EL element, and includes a substrate 2, an anode 3, a hole injection layer 4, an organic light emitting layer 5, an electron transport layer 6, a cathode 7, and a sealing layer 8.
- the substrate 2 is made of alkali-free glass and serves as a base material for the organic EL element.
- a TFT (thin film transistor) layer (not shown) for driving the organic EL element is formed on the surface of the substrate 2, on which an anode 3, an organic functional layer (a hole injection layer 4, an organic light emitting layer 5). ,
- the electron transport layer 6) and the cathode 7 are sequentially laminated, and the organic EL element 1 is manufactured.
- the material of the substrate 2 includes soda glass, non-fluorescent glass, phosphate glass, borate glass, quartz, acrylic resin, styrene resin, polycarbonate resin, epoxy resin, polyethylene, polyester, silicon resin, An insulating material such as alumina can also be used.
- the anode 3 has a function of injecting holes into the hole injection layer 4.
- Al aluminum
- Al is used as the material of the anode 3 and is formed on the substrate 2 with a thickness of about 400 [nm] by sputtering.
- the material of the anode 3 is Ag (silver), aluminum alloy, Mo (molybdenum), APC (silver, palladium, copper alloy), ARA (silver, rubidium, gold alloy), MoCr (molybdenum and chromium). It is also possible to use a light-reflective conductive material such as an alloy), MoW (alloy of molybdenum and tungsten), NiCr (alloy of nickel and chromium), ACL (alloy of aluminum, cobalt, germanium, lanthanum).
- the hole injection layer 4 has a function of promoting injection and transport of holes from the anode 3 to the organic light emitting layer 5.
- WOX tungsten oxide
- tungsten oxide is used as the material of the hole injection layer 4 and is formed on the anode 3 with a thickness of about 14 [nm] by sputtering.
- the material of the hole injection layer 4 includes an oxide such as silver (Ag), molybdenum (Mo), chromium (Cr), vanadium (V), nickel (Ni), iridium (Ir), or PEDOT (A conductive polymer material such as a mixture of polythiophene and polystyrene sulfonic acid) can also be used.
- an oxide such as silver (Ag), molybdenum (Mo), chromium (Cr), vanadium (V), nickel (Ni), iridium (Ir), or PEDOT (A conductive polymer material such as a mixture of polythiophene and polystyrene sulfonic acid) can also be used.
- the organic light emitting layer 5 is a part that emits light by recombination of carriers (holes and electrons).
- An organic light emitting polymer is used as the material of the organic light emitting layer 5 and is formed on the hole injection layer 4 with a thickness of about 80 [nm] by an ink jet method.
- Examples of the material of the organic light emitting layer 5 include polyparaphenylene vinylene (PPV), polyfluorene, and oxinoid compounds, perylene compounds, coumarin compounds, azacoumarins described in, for example, a patent publication (JP-A-5-163488).
- PV polyparaphenylene vinylene
- polyfluorene polyfluorene
- oxinoid compounds perylene compounds
- coumarin compounds azacoumarins described in, for example, a patent publication (JP-A-5-163488).
- the electron transport layer 6 is composed of an electron transport material 6 a and an n-type dopant 6 b containing an electron donating substance, and has a function of transporting electrons injected from the cathode 7 to the organic light emitting layer 5.
- an organic monomer having an electron transporting property is used for the electron transporting material 6a
- Ba (barium) is used for the n-type dopant 6b, and about 35 [ nm].
- FIG. 2 is a graph showing the relationship between the Ba doping concentration of the organic EL element and the light emission efficiency of the organic light emitting layer 5.
- the materials, deposition methods, and layer thicknesses shown in this embodiment are used to determine the substrate 2, the anode 3, the hole injection layer 4, the organic light emitting layer 5, the electron transport layer 6, the cathode 7, and the sealing layer 8.
- Each layer is formed to produce a plurality of organic EL elements having different Ba doping concentrations, and the light emission efficiency of each organic EL element is measured.
- the horizontal axis represents the Ba doping concentration [wt%] based on the total weight of the electron transport layer 6, and the vertical axis represents the luminous efficiency [cd / A] of the organic light emitting layer 5.
- the luminous efficiency on the vertical axis is normalized by the luminous efficiency at a doping concentration of 30 [wt%].
- the luminous efficiency of the organic light emitting layer 5 increases as the doping concentration of Ba increases. Further, when the doping concentration of Ba is 15 [wt%], the light emission efficiency of the organic light emitting layer 5 is maximized. In the range where the Ba concentration exceeds 15 [wt%], the luminous efficiency of the organic light emitting layer 5 decreases as the Ba doping concentration increases.
- the injection amount of electrons from the electron transport layer 6 to the organic light emitting layer 5 is within the range where the Ba concentration is less than 15 wt%. Since the amount of holes injected from the hole injection layer 4 into the organic light emitting layer 5 is small, it is considered that the luminous efficiency of the organic light emitting layer 5 increased as the Ba doping concentration increased. Further, when the doping concentration of Ba is 15 [wt%], the injection amount of electrons from the electron transport layer 6 to the organic light emitting layer 5 and the injection amount of holes from the hole injection layer 4 to the organic light emitting layer 5 are as follows.
- the light emission efficiency of the organic light emitting layer 5 is maximized because the amounts are substantially the same. Further, in the range where the Ba concentration exceeds 15 [wt%], the injection amount of electrons from the electron transport layer 6 to the organic light emitting layer 5 becomes the injection amount of holes from the hole injection layer 4 to the organic light emitting layer 5. It is considered that the light emission efficiency of the organic light emitting layer 5 is reduced as the doping concentration of Ba is increased because of a larger amount.
- the relationship between the doping concentration of Ba of the organic EL element and the luminous efficiency of the organic light emitting layer can be applied to other general organic EL elements.
- Ba is doped in the electron transport layer 6 at a concentration higher than the doping concentration at which the light emission efficiency of the organic light emitting layer 5 is maximized. That is, Ba is doped in the electron transport layer 6 at a concentration exceeding 15 [wt%].
- organic materials such as an oxadiazole derivative (OXD), a triazole derivative (TAZ), and a phenanthroline derivative (BCP, Bphen), can also be used for the material of the electron transport material 6a.
- OXD oxadiazole derivative
- TEZ triazole derivative
- BCP phenanthroline derivative
- an alkali metal such as Li (lithium), Na (sodium), or K (potassium), or an alkaline earth metal such as Mg (magnesium) or Ca (calcium) may be used. it can.
- the cathode 7 has a function of injecting electrons into the electron transport layer 6.
- the material of the cathode 7 is ITO (indium tin oxide), and is formed on the electron transport layer 6 with a thickness of about 35 [nm] by sputtering.
- the cathode 7 is made of a transparent conductive material made of an oxide containing at least one of In, Ti, Zn, and Sn, such as IZO (indium zinc oxide), ZnO (zinc oxide), and TiO2 (titanium oxide). It can also be used.
- IZO indium zinc oxide
- ZnO zinc oxide
- TiO2 titanium oxide
- the sealing layer 8 has a function of sealing the organic functional layer (the hole injection layer 4, the organic light emitting layer 5, and the electron transport layer 6) and protecting the organic functional layer from moisture or oxygen existing outside.
- SI3N4 silicon nitride
- SiO2 silicon oxide
- SiON silicon oxynitride
- the organic EL element 1 includes (1) a step of forming an anode 3 (anode formation step), (2) a step of forming a hole injection layer 4 (hole injection layer formation step), and (4) an organic light emitting layer 5. Step of forming (organic light emitting layer forming step), (5) Step of forming electron transport layer 6 (electron transport layer forming step), (6) Step of forming cathode 7 (cathode forming step), (7) Sealing It is manufactured through a step of forming the layer 8 (sealing layer forming step).
- each layer is formed using various film forming methods such as a sputtering method, an inkjet method, a vacuum vapor deposition method, and a chemical vapor deposition method.
- film forming methods such as a sputtering method, an inkjet method, a vacuum vapor deposition method, and a chemical vapor deposition method.
- FIG. 3 is a cross-sectional view illustrating the configuration of the organic EL element according to the first embodiment in a state where a crack is generated in the sealing layer.
- the foreign material 10 is mixed in the electron transport layer 6, and a part of the electron transport layer 6 is raised upward (Y direction side).
- the organic EL element 1 is manufactured by sequentially laminating an anode 3, a hole injection layer 4, an organic light emitting layer 5, an electron transport layer 6, a cathode 7, and a sealing layer 8 on a substrate 2. If the layer is not formed flat and irregularities are formed on the surface thereof, the layer formed thereon may crack. In the example shown in the figure, cracks 11 a and 11 b are generated in a part of the sealing layer 8 located above the foreign material 10.
- FIG. 4 is an enlarged cross-sectional view of a portion surrounded by a broken line A in FIG.
- water or gas or the like enters from the cracks 11a and 11b.
- the infiltrated water or gas passes through the cathode 7 to reach the electron transport layer 6 and reacts with the n-type dopant 6 b doped in the electron transport layer 6.
- the doping concentration of the n-type dopant 6 b in the electron transport layer 6 gradually decreases toward the position closest to the cracks 11 a and 11 b in the electron transport layer 6.
- the n-type dopant 6b reacted with water or gas loses electron donating properties. For this reason, the electron transfer complex formed between the electron transport material 6a-n type dopant 6b is decomposed, and the electron mobility of the electron transport layer 6 is lowered.
- the “concentration of n-type dopant” refers to the concentration of n-type dopant existing as an electron transfer complex, and does not include the concentration of n-type dopant reacted with water or gas.
- the n-type dopant is Ba
- the concentration of Ba that reacts with water or gas and exists as Ba (OH) 2 (barium hydroxide) or the like is not included.
- the organic EL element 1 has a defective light emission region B in which the light emission luminance is reduced or non-light emission, a bright light emission region C in which the light emission luminance of the organic light emitting layer 5 is improved, and a crack.
- Defective light emitting area B is located in the vicinity of the cracks 11a and 11b. In the vicinity immediately below the cracks 11a and 11b, the amount of water or gas that permeates is large, so the doping concentration of the n-type dopant 6b is 0 [wt%] or very small. For this reason, the electron mobility of the electron carrying layer 6 falls significantly, and the luminous efficiency of the organic light emitting layer 5 falls. As a result, the light emission luminance of the organic light emitting layer 5 decreases or no light is emitted.
- the normal light emitting region D is located at a certain distance from the cracks 11a and 11b, and water or gas entering from the cracks 11a and 11b does not reach. For this reason, the doping concentration of the n-type dopant 6b is constant before and after the generation of the cracks 11a and 11b, and the light emission luminance of the normal light emission region D does not change.
- the bright light emitting area C is located between the defective light emitting area B and the normal light emitting area D.
- the n-type dopant 6b is doped in the electron transport layer 6 at a concentration higher than the doping concentration at which the light emission efficiency of the organic light emitting layer 5 is maximized. For this reason, even if the water or gas that has entered through the cracks 11a and 11b reacts with the n-type dopant 6b to reduce the doping concentration, the luminous efficiency of the organic light emitting layer 5 is improved if the amount of the reduction is small.
- the doping concentration of the n-type dopant 6b is reduced and the light emitting efficiency of the organic light emitting layer 5 is improved, thereby improving the light emission luminance.
- a light emitting region C is formed.
- FIG. 5 is a diagram showing the relationship among the position in the X direction of the organic EL element according to the first embodiment, the doping concentration of the n-type dopant, and the light emission efficiency of the organic light emitting layer. It is a figure which shows the relationship between the doping density
- FIG. 5A shows the relationship between the doping concentration of Ba shown in FIG. 2 and the luminous efficiency of the organic light emitting layer 5 with the vertical axis and the horizontal axis switched, and the vertical axis in FIG.
- the scale of the axis is drawn in accordance with the scale of the vertical axis in FIG. 5A and 5B, the relationship between the position in the X direction of the organic EL element 1 shown in FIG. 5C and the light emission efficiency of the organic light emitting layer 5 can be obtained.
- X5 indicates the position of the crack 11a. In the region on the left side of X5, the doping concentration of Ba gradually decreases toward X5.
- X1 indicates a position where the doping concentration of Ba starts to decrease.
- the doping concentration is about 30 [wt%]
- the light emission efficiency of the organic light emitting layer 5 at that position is about 1.1 [cd / A].
- a region on the left side of the position X1 is a normal light emitting region D.
- the doping concentration is about 15 [wt%] or more and about 30 [wt%] or less, as the doping concentration of Ba decreases, Luminous efficiency is improved. For this reason, the light emission efficiency of the organic light emitting layer 5 improves as it goes to the right side of X1.
- X2 indicates a position where the luminous efficiency of the organic light emitting layer 5 is maximized.
- the doping concentration of Ba is reduced to about 15 [wt%], and the light emission efficiency of the organic light emitting layer 5 is about 1.6 [cd / A].
- the luminous efficiency of the organic light emitting layer 5 decreases as the doping concentration of Ba decreases. For this reason, the luminous efficiency of the organic light emitting layer 5 decreases as it goes to the right side of X2.
- X3 indicates a position where the light emitting efficiency of the organic light emitting layer 5 is approximately the same as the light emitting efficiency in the normal light emitting region D.
- the doping concentration is about 5 [wt%]
- the light emission efficiency of the organic light emitting layer 5 at that position is about 1.1 [cd / A].
- a region between X2 and X3 is a bright light emitting region C.
- X4 indicates a position where the doping concentration of Ba is lowered and the concentration becomes 0 [wt%].
- X11 indicates a position where the light emitting efficiency of the organic light emitting layer 5 is 0 [cd / A].
- a region between X3 and X11 is a luminance reduction region B1 in which the emission luminance is lower than before the cracks 11a and 11b are generated.
- X6 indicates the position of the crack 11b. In the region on the right side of X6, the doping concentration of Ba gradually decreases toward X6. The change in the doping concentration of Ba in the region on the right side of X6 and the change in the light emission efficiency of the organic light emitting layer 5 are the same as the change in the region on the left side of X5.
- X10 indicates a position where the doping concentration of Ba starts to decrease
- X9 indicates a position where the light emission efficiency of the organic light emitting layer 5 becomes maximum
- X8 indicates light emission in the normal light emitting region D where the light emission efficiency of the organic light emitting layer 5 is normal. It shows the position where the efficiency is about the same.
- X7 indicates a position where the doping concentration of Ba decreases and the concentration becomes 0 [wt%]
- X12 indicates a position where the luminous efficiency of the organic light emitting layer 5 becomes 0 [cd / A].
- the region on the right side of the position of X10 is the normal light emitting region D
- the region between X10 and X8 is the bright light emitting region C
- the region between X8 and X12 is the luminance reduction region B1.
- a region between X11 and X12 is a non-light emitting region B2.
- the defective light emitting region B is composed of a luminance reduction region B1 and a non-light emitting region B2.
- the doping concentration of Ba doped in the electron transport layer 6 is higher than the doping concentration at which the light emitting efficiency of the organic light emitting layer 5 is maximized, so that it is adjacent to the defective light emitting region B.
- the luminous efficiency is improved by decreasing the doping concentration of Ba. Since the light emission efficiency of the region C adjacent to the defective light emitting region B is improved and the light emission luminance is improved, the apparent size of the defective light emitting region B is reduced, and the defective light emitting region B is less noticeable to the user.
- FIG. 6 is a diagram showing the relationship among the position of the conventional organic EL element in the X direction, the doping concentration of the n-type dopant, and the light emission efficiency of the organic light emitting layer, where (a) shows the conventional organic EL element. It is a figure which shows the relationship between the doping density
- FIG. 6A shows the relationship between the doping concentration of Ba shown in FIG. 2 and the luminous efficiency of the organic light emitting layer with the vertical axis and the horizontal axis switched, and the vertical axis of FIG.
- the scale is drawn in accordance with the scale on the vertical axis in FIG. 6A and 6B, the relationship between the position in the X direction of the conventional organic EL element shown in FIG. 6C and the light emission efficiency of the organic light emitting layer is obtained.
- the n-type dopant is doped in the electron transport layer in order to improve the electron mobility of the electron transport layer and increase the light emission efficiency of the organic light emitting layer. Therefore, conventionally, an n-type dopant has been doped in the electron transport layer at a doping concentration that is lower than the doping concentration that maximizes the luminous efficiency of the organic light emitting layer or that maximizes the luminous efficiency of the organic light emitting layer.
- Ba is doped in the electron transport layer at a concentration of about 10 [wt%].
- X21 indicates the position where the doping concentration of Ba begins to decrease.
- the doping concentration is about 10 [wt%]
- the light emission efficiency of the organic light emitting layer 5 at that position is about 1.5 [cd / A].
- a region on the left side of the position of X21 is a normal light emitting region D1.
- the luminous efficiency of the organic light emitting layer decreases as the doping concentration of Ba decreases. For this reason, as it goes to the right side of X21, the luminous efficiency of the organic light emitting layer decreases.
- X22 indicates a position where the doping concentration of Ba is lowered and the concentration becomes 0 [wt%].
- X25 indicates a position where the light emitting efficiency of the organic light emitting layer is 0 [cd / A].
- a region between X21 and X25 is a luminance reduction region B4 in which the emission luminance is lower than before the cracks 11a and 11b are generated.
- the doping concentration of Ba gradually decreases toward X6.
- the change in the doping concentration of Ba in the region on the right side of X6 and the change in the light emission efficiency of the organic light emitting layer are the same as the change in the region on the left side of X5.
- X24 indicates the position where the doping concentration of Ba begins to decrease
- X23 indicates the position where the doping concentration of Ba decreases and the concentration becomes 0 wt%
- X26 indicates the luminous efficiency of the organic light emitting layer. The position to be 0 [cd / A] is shown.
- the region on the right side of the position of X24 is the normal light emitting region D1
- the region between X24 and X26 is the luminance reduction region B4
- the region between X25 and X26 is the non-light emitting region B3.
- the defective light emitting region B3 is composed of a luminance reduction region B4 and a non-light emitting region B5.
- the length from the position X6 of the crack 11b to the position X12 where the light emission efficiency of the organic light emitting layer is 0 [cd / A] in the organic EL element 1 is from the position X5 of the crack 11a to the organic EL element 1. It is longer than the length to the position X26 where the luminous efficiency of the organic light emitting layer is 0 [cd / A]. Therefore, the non-light-emitting region B2 in the organic EL element 1 is smaller than the non-light-emitting region B5 in the conventional organic EL element.
- the luminous efficiency of the normal light emitting region D of the organic EL element 1 is lower than the luminous efficiency of the normal light emitting region D1 of the conventional organic EL element. Therefore, the length from the position X3 where the light emission efficiency in the organic EL element 1 is approximately the same as the light emission efficiency in the normal light emission region D to the position X11 where the light emission efficiency of the organic light emitting layer is 0 [cd / A] is In the conventional organic EL element, the light emission efficiency is shorter than the length from the position X21 where the light emission efficiency is about the same as the light emission efficiency in the normal light emission region D1 to the position X25 where the light emission efficiency of the organic light emitting layer is 0 [cd / A]. Accordingly, the luminance reduction region B1 in the organic EL element 1 is smaller than the non-light emitting region B2 in the conventional organic EL element.
- the organic EL element 1 since the organic EL element 1 has a smaller non-light-emitting area and a lower brightness area than the conventional organic EL element, the size of the defective light-emitting area including the non-light-emitting area and the lower brightness area is also higher than that of the conventional organic EL element. It is smaller than the organic EL element. (3) Apparent size of defective light emitting region The bright light emitting region C of the organic EL element 1 is adjacent to the defective light emitting region B. Since the light emission luminance of the bright light emission region C is high and the darkness of the defective light emission region B is interpolated, the apparent size of the defective light emission region B is reduced. For this reason, the defective light emission region B is less noticeable to the user.
- FIG. 7 is a diagram showing an enlarged photograph of a state in which a foreign substance is mixed and a defective light emitting region is generated.
- FIG. 7A is a diagram showing an enlarged photograph of the defective light emitting region when the doping concentration of Ba is about 40 [wt%].
- B is a figure which shows the enlarged photograph of the foreign material which causes the defective light emission area
- (c) is the defect light emission in case the doping concentration of Ba is about 20 [wt%]. It is a figure which shows the enlarged photograph of an area
- the foreign matter is present in a portion surrounded by a broken line, and the size thereof is about 30 [ ⁇ m].
- the size of the defective light emitting region is about 2 ⁇ 2 for four pixels.
- the size of the defective light emitting region is about 3 ⁇ 3 of 9 pixels.
- the doping concentration of Ba is about 5 [wt%] the size of the defective light emitting region is about 5 ⁇ 5 for 25 pixels.
- FIG. 8 is a diagram showing the relationship between the Ba doping concentration of the organic EL element and the apparent number of defective light emitting regions.
- the horizontal axis represents the Ba doping concentration [wt%] based on the total weight of the electron transport layer, and the vertical axis represents the number of apparent defective light emitting regions [pieces].
- the defective light emission in which the light emission luminance is reduced or non-light emission is performed. The number of areas is counted visually.
- the doping concentration of Ba increases, the number of apparent defective light emitting regions decreases.
- the doping concentration of Ba is about 40 [wt%], the apparent defective light emitting region is obtained. It can be seen that the number of is zero.
- FIG. 9 is a diagram showing the relationship between the length of the diameter of a foreign substance that causes the defective light emitting region to occur and the Ba doping concentration of the organic EL element when a visible defective light emitting region is generated.
- the horizontal axis represents the Ba doping concentration [wt%] based on the total weight of the electron transport layer, and the vertical axis represents the diameter [ ⁇ m] of the foreign matter.
- an organic EL element having a Ba doping concentration of about 5 [wt%] may generate a visually defective light emitting region.
- an organic EL element having a Ba doping concentration of about 30 [wt%] does not generate a visible defective light emitting region. I understand that.
- the straight line shown in FIG. 9 is obtained by connecting the lengths of the diameters of the smallest foreign matters in which a visually defective light emitting region is generated at each Ba doping concentration by logarithmic approximation.
- the straight line is expressed by the following relational expression, where the doping concentration of Ba is N [wt%], and the diameter of the smallest foreign matter in which a visible defective light emitting region is generated is D [ ⁇ m].
- the diameter of a foreign substance that can be easily removed is about 20 [ ⁇ m] or more. Even if foreign matter having a diameter that is difficult to remove is less than about 20 [ ⁇ m], a visible light emitting region does not occur. From FIG. 9 and the above formula, the doping concentration of Ba is about 25 [ wt%] or more.
- the present disclosure can also be implemented as an organic EL display panel including the organic EL element according to the above-described embodiment and an organic EL display device including the organic EL panel.
- FIG. 10 is an external view showing an organic EL display device according to a modification.
- FIG. 11 is a schematic block diagram of a configuration of an organic EL display device according to a modification.
- the organic EL display device 100 includes an organic EL display panel 110 and a drive control unit 120 connected thereto.
- the organic EL display panel 110 includes a plurality of organic EL elements according to the above-described embodiments arranged in a matrix, for example.
- the drive control unit 120 is composed of four drive circuits 121 to 124 and a control circuit 125.
- the organic EL display device 100 and the organic EL display panel 110 as described above, even if an undesired defective light emitting region occurs, the light emission efficiency of the region adjacent to the defective light emitting region is improved and the light emission luminance is improved. . For this reason, the apparent size of the defective light emitting area is reduced, and the defective light emitting area is less noticeable to the user.
- the doping concentration of Ba doped into the electron transport layer is preferably 50 wt% or less. This is to ensure a certain light emission efficiency in the normal light emission region. Further, when the doping concentration of Ba is 50 [wt%] or less, there is a low possibility that leakage current will occur.
- the organic EL element is composed of a substrate, an anode, a hole injection layer, an organic light emitting layer, an electron transport layer, a cathode, and a sealing layer. It is not limited. Any organic EL element having an anode, a cathode, an organic light-emitting layer, and an electron transport layer that is provided between the cathode and the organic light-emitting layer and transports electrons from the cathode to the organic light-emitting layer may be mentioned here.
- the structure including an organic functional layer other than the above may be used.
- an electron injection layer having a function of promoting the injection of electrons from the cathode to the electron transport layer may be provided between the cathode and the electron transport layer.
- the material for the electron injection layer includes low work function metals such as lithium, barium, calcium, potassium, cesium, sodium, and rubidium, low work function metal salts such as lithium fluoride, and low work function metal oxides such as barium oxide. Etc. are preferred.
- a hole transport layer having a function of transporting holes injected from the anode to the organic light emitting layer may be provided between the organic light emitting layer and the hole injection layer.
- the material for the hole transport layer include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives described in Patent Publication (JP-A-5-163488), phenylenediamine Derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, polyphyrin compounds, aromatic tertiary amine compounds, styrylamine compounds, butadiene compounds, polystyrene derivatives, hydrazone derivatives , Triphenylmethane derivatives, tetraphenylbenzine derivative
- a resin layer for protecting the organic EL element may be provided above the sealing layer.
- a resin material such as an epoxy resin, an acrylic resin, or a urethane resin is suitable for the material of the resin layer.
- a so-called top emission type organic EL element that extracts light from the cathode side is shown, but the present disclosure is not necessarily limited to this case.
- a so-called bottom emission type organic EL element that extracts light from the substrate side may be used.
- a light-transmitting material such as ITO or IZO is used for the anode.
- each layer of the organic EL element is formed by using a film forming method such as a sputtering method, an ink jet method, a vacuum vapor deposition method, a chemical vapor deposition method, or the like has been described. Is not necessarily limited to this case.
- the film forming method described above is an example, and the present invention is not limited to this.
- the organic EL element according to one embodiment of the present invention can be used for, for example, an organic EL element used as a display device for a home or public facility, or for business use, a television device, a portable electronic device, or the like. .
Abstract
Description
本開示の一態様である有機EL素子は、陽極と、陰極と、前記陽極と前記陰極との間に設けられた有機発光層と、前記陰極と前記有機発光層との間に設けられた電子輸送層とを有する有機EL素子であって、前記電子輸送層は、電子供与性物質を含むn型ドーパントがドープされてなり、そのドープ濃度は、前記有機発光層の発光効率が最大となるドープ濃度よりも高い。
以下では、本開示の実施の形態について、図面を参照しながら説明する。
図1は、実施の形態1にかかる有機EL素子の構成を示す断面図である。有機EL素子1は、所謂トップエミッション型の有機EL素子であって、基板2、陽極3、正孔注入層4、有機発光層5、電子輸送層6、陰極7、封止層8を備える。
基板2は、無アルカリガラスからなり、有機EL素子の基材としての役割を果たす。基板2の表面には有機EL素子を駆動するためのTFT(薄膜トランジスタ)層(不図示)が形成されており、その上に、陽極3、有機機能層(正孔注入層4、有機発光層5、電子輸送層6)、陰極7が順次積層され、有機EL素子1が製造される。
陽極3は、正孔を正孔注入層4に注入する機能を有する。陽極3の材料にはAl(アルミニウム)が用いられ、スパッタリング法により基板2の上に約400[nm]の厚みで形成されている。
正孔注入層4は、陽極3から有機発光層5への正孔の注入および輸送を促進させる機能を有する。正孔注入層4の材料には、WOX(酸化タングステン)が用いられ、スパッタリング法により陽極3の上に約14[nm]の厚みで形成されている。
有機発光層5は、キャリア(正孔と電子)の再結合による発光を行う部位である。有機発光層5の材料には、有機発光ポリマーが用いられ、インクジェット法により正孔注入層4の上に約80[nm]の厚みで形成されている。
電子輸送層6は、電子輸送性材料6aおよび電子供与性物質を含むn型ドーパント6bからなり、陰極7から注入された電子を有機発光層5に輸送する機能を有する。本実施の形態では、電子輸送性材料6aには電子輸送性を有する有機モノマーを用い、n型ドーパント6bにはBa(バリウム)を用い、真空蒸着法により有機発光層5の上に約35[nm]の厚みで形成されている。電子輸送性材料6aにn型ドーパント6bをドープすることで、電子輸送性材料6a‐n型ドーパント6b間で電子移動が起こり、電子移動錯体(CT錯体)が形成される。これにより、電子輸送層6の電子移動度が向上するため、陰極7から注入された電子を効率的に有機発光層5に輸送することができる。
陰極7は、電子を電子輸送層6に注入する機能を有する。陰極7の材料には、ITO(酸化インジウムスズ)が用いられ、スパッタリング法により電子輸送層6の上に約35[nm]の厚みで形成されている。
封止層8は、有機機能層(正孔注入層4、有機発光層5、電子輸送層6)を封止し、外部に存在する水分または酸素等から、有機機能層を保護する機能を有する。封止層8の材料には、SI3N4(窒化ケイ素)が用いられ、化学気相成長法(CVD:Chemical Vapor Deposition)により陰極7の上に約600[nm]の厚みで形成されている。
有機EL素子1は、(1)陽極3を形成する工程(陽極形成工程)、(2)正孔注入層4を形成する工程(正孔注入層形成工程)、(4)有機発光層5を形成する工程(有機発光層形成工程)、(5)電子輸送層6を形成する工程(電子輸送層形成工程)、(6)陰極7を形成する工程(陰極形成工程)、(7)封止層8を形成する工程(封止層形成工程)を経て製造される。各工程では、スパッタリング法、インクジェット法、真空蒸着法、化学気相成長法等の各種の成膜方法を用いて、各層が形成される。クリーンな雰囲気中で各層が形成されるものの、製造工程中に各層への異物混入をゼロにすることは困難である。製造工程中に異物が混入した場合、各層に亀裂等が生じる場合がある。
以下では、封止層に亀裂が生じた状態における、有機EL素子1と上記の従来の有機EL素子とを比較する。
(1)非発光領域の大きさ
有機EL素子1は、従来の有機ELと比較して、電子輸送層にドープするBa濃度が高いため、亀裂11aの位置X5から有機EL素子1において有機発光層の発光効率が0[cd/A]となる位置X11までの長さは、亀裂11aの位置X5から有機EL素子1において有機発光層の発光効率が0[cd/A]となる位置X25までの長さよりも長い。これと同様に、亀裂11bの位置X6から有機EL素子1において有機発光層の発光効率が0[cd/A]となる位置X12までの長さは、亀裂11aの位置X5から有機EL素子1において有機発光層の発光効率が0[cd/A]となる位置X26までの長さよりも長い。従って、有機EL素子1における非発光領域B2は、上記の従来の有機EL素子における非発光領域B5よりも小さい。
(2)輝度低下領域の大きさ
有機EL素子1の正常発光領域Dの発光効率は、従来の有機EL素子の正常発光領域D1よりも発光効率よりも低い。このため、有機EL素子1において発光効率が正常発光領域Dにおける発光効率と同程度になる位置X3から、有機発光層の発光効率が0[cd/A]となる位置X11までの長さは、従来の有機EL素子において発光効率が正常発光領域D1における発光効率と同程度になる位置X21から、有機発光層の発光効率が0[cd/A]となる位置X25までの長さより短い。従って、有機EL素子1における輝度低下領域B1は、上記の従来の有機EL素子における非発光領域B2よりも小さい。
(3)不良発光領域のみかけ上の大きさ
有機EL素子1の明発光領域Cは不良発光領域Bに隣接している。明発光領域Cの発光輝度が高く、不良発光領域Bの暗さを補間するため、不良発光領域Bの見かけ上の大きさは小さくなる。このため、不良発光領域Bがユーザに目立ちにくくなる。
本実施の形態にかかる有機EL素子の上記効果を確かめるため、以下の検証実験を行った。
上記の実施の形態では、Baを電子輸送層に、15[wt%]を越える濃度でドープする場合を示した。このBaのドープ濃度に関しては、Baを電子輸送層に、25[wt%]以上の濃度でドープすることがより好ましい。その理由を以下に示す。
一般に、除去が容易な異物の直径の大きさは、約20[μm]以上である。除去が難しい直径の大きさが約20[μm]未満の異物が混入したとしても、目視可能な不良発光領域が発生しないためには、図9および上記数式から、Baのドープ濃度が約25[wt%]以上であればよいことが分かる。
本開示は、上記の実施の形態にかかる有機EL素子を備える有機EL表示パネル、およびその有機ELパネルを備える有機EL表示装置としても実施可能である。
なお、上記の実施の形態に基づいて説明してきたが、本開示は上記の実施の形態に限定されないことはもちろんである。以下のような場合も本開示に含まれる。
2 基板
3 陽極
4 正孔注入層
5 有機発光層
6 電子輸送層
6a 電子輸送性材料
6b n型ドーパント
7 陰極
8 封止層
10 異物
11a、11b 亀裂
100 有機EL表示装置
110 有機EL表示パネル
Claims (8)
- 陽極と、陰極と、前記陽極と前記陰極との間に設けられた有機発光層と、前記陰極と前記有機発光層との間に設けられた電子輸送層とを有する有機EL素子であって、
前記電子輸送層は、電子供与性物質を含むn型ドーパントがドープされてなり、そのドープ濃度は、前記有機発光層の発光効率が最大となるドープ濃度よりも高い
ことを特徴とする有機EL素子。 - 前記陰極を挟んで前記電子輸送層とは反対側に設けられた封止層をさらに有し、
前記封止層に不所望の亀裂が生じた場合において、
前記n型ドーパントが、前記亀裂から浸入した水またはガスと反応することにより、そのドープ濃度が前記電子輸送層における前記亀裂に最も近い位置に向かって漸減しており、
前記n型ドーパントのドープ濃度が漸減している領域に対応する前記有機発光層の領域には、発光効率が最大となる領域が存在する
ことを特徴とする請求項1に記載の有機EL素子。 - 前記n型ドーパントは、アルカリ金属、またはアルカリ土類金属である
ことを特徴とする請求項1に記載の有機EL素子。 - 前記n型ドーパントは、バリウムである
ことを特徴とする請求項1に記載の有機EL素子。 - 前記バリウムのドープ濃度は、15wt%より高い
ことを特徴とする請求項4に記載の有機EL素子。 - 前記バリウムのドープ濃度は、25wt%以上である
ことを特徴とする請求項4に記載の有機EL素子。 - 前記バリウムのドープ濃度は、50wt%以下である
ことを特徴とする請求項5に記載の有機EL素子。 - 請求項1ないし7のいずれか1項に記載の有機EL素子を備える
ことを特徴とする有機EL表示パネル。
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