JP3852509B2 - Electroluminescent device and manufacturing method thereof - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electroluminescent element and a manufacturing method thereof, for example, a self-luminous flat display, and particularly suitable for a display element or a luminescent device such as an organic electroluminescent color display using an organic thin film as an electroluminescent layer. The present invention relates to an electroluminescent element and a method for manufacturing the same.
[0002]
[Prior art]
In recent years, the importance of human-machine interfaces has been increasing, especially in multimedia-oriented products. In order for humans to operate a machine more comfortably and efficiently, it is necessary to extract information from the machine to be operated in a succinct, instantaneous, and sufficient amount without error. Research has been conducted on display elements.
[0003]
In addition, with the miniaturization of machines, the demand for miniaturization and thinning of display elements is increasing day by day.
[0004]
For example, downsizing of laptop information processing devices that are integrated with display elements, such as notebook personal computers and notebook word processors, has made remarkable progress, and as a result, technologies related to liquid crystal displays that are display elements Innovation is also great.
[0005]
Today, liquid crystal displays are used as interfaces for various products, and are often used not only in laptop-type information processing equipment but also in products that we use everyday, such as small TVs, watches, and calculators. .
[0006]
These liquid crystal displays have been studied as the center of display elements as a human-machine interface, ranging from small to large capacity display devices, taking advantage of the low-voltage driving and low power consumption of liquid crystals.
[0007]
However, since this liquid crystal display is not self-luminous, it requires a backlight, and this backlight drive requires more power than driving the liquid crystal. There are restrictions on use.
[0008]
Furthermore, since the viewing angle is narrow, the liquid crystal display is not suitable for a large display element such as a large display.
[0009]
In addition, since the liquid crystal display is a display method based on the alignment state of liquid crystal molecules, it is considered that the contrast changes depending on the angle even in the viewing angle.
[0010]
From the viewpoint of the driving method, the active matrix method, which is one of the driving methods, exhibits a response speed sufficient for handling moving images. However, since a TFT (thin film transistor) driving circuit is used, the screen size is increased due to pixel defects. Is difficult.
[0011]
In a liquid crystal display, the simple matrix method, which is another driving method, is low in cost and relatively easy to increase the screen size, but has a problem that it does not have a response speed sufficient for handling moving images. is there.
[0012]
On the other hand, plasma display elements, inorganic electroluminescent elements, organic electroluminescent elements and the like have been studied as self-luminous display elements.
[0013]
A plasma display element uses plasma emission in a low-pressure gas for display and is suitable for an increase in size and capacity, but has problems in terms of thickness reduction and cost. In addition, a high voltage AC bias is required for driving, which is not suitable for portable devices.
[0014]
As the inorganic electroluminescent element, a green light emitting display or the like has been commercialized. However, like the plasma display element, it is AC bias driving, and requires several hundred volts for driving, and lacks practicality.
[0015]
However, with the development of technology, we have succeeded in emitting the three primary colors R (red), G (green), and B (blue) necessary for color display, but because of inorganic materials, light emission by molecular design etc. It is difficult to control the wavelength and the like, and it seems difficult to achieve full color.
[0016]
On the other hand, the electroluminescence phenomenon due to organic compounds has been studied for a long time since the discovery of the light emission phenomenon due to carrier injection into anthracene single crystals that generate strong fluorescence in the early 1960s. And since it was a single crystal, it was carried out as a basic study of carrier injection into an organic material.
[0017]
However, since Tang et al. Of Eastman Kodak in 1987 announced an organic thin film electroluminescent device having an amorphous light emitting layer capable of low voltage drive and high luminance emission, R, G, B in various directions. Research and development of these three primary colors, such as light emission, stability, brightness increase, layered structure, and production method, are actively conducted.
[0018]
Furthermore, as a characteristic of organic materials, various new materials have been invented by molecular design, etc., and have excellent characteristics such as direct current low voltage driving, thinness, self-luminous property, etc. Applied research is also being actively conducted.
[0019]
An organic electroluminescent element (hereinafter sometimes referred to as an organic EL element) has a film thickness of 1 μm or less, and converts electric energy into light energy by injecting a current to emit light in a planar shape. It has ideal characteristics as a light-emitting display device.
[0020]
FIG. 34 shows an example of a conventional organic EL element 10. The organic EL element 10 includes an ITO (Indium Tin Oxide) transparent electrode 5, a hole transport layer 4, a light emitting layer 3, an electron transport layer 2, and a cathode (for example, an aluminum electrode) 1 on a transparent substrate (for example, a glass substrate) 6. For example, the films are sequentially formed by vacuum deposition.
[0021]
Then, by selectively applying a DC voltage 7 between the transparent electrode 5 as the anode and the cathode 1, holes as carriers injected from the transparent electrode 5 pass through the hole transport layer 4 and from the cathode 1. The injected electrons move through the electron transport layer 2 and electron-hole recombination occurs. From this, light emission 8 having a predetermined wavelength is generated and can be observed from the transparent substrate 6 side.
[0022]
For the light emitting layer 3, for example, a light emitting material such as anthracene, naphthalene, phenanthrene, pyrene, chrysene, perylene, butadiene, coumarin, acridine, stilbene, or the like may be used. This can be contained in the electron transport layer 2.
[0023]
FIG. 35 shows another conventional example, in which the light emitting layer 3 is omitted, and the electron transport layer 2 contains the light emitting material as described above, and a predetermined wavelength from the interface between the electron transport layer 2 and the hole transport layer 4. The organic EL element 20 comprised so that the light emission 18 of this may be produced is shown.
[0024]
FIG. 36 shows a specific example of the organic EL element. That is, a laminate of each organic layer (hole transport layer 4, light-emitting layer 3 or electron transport layer 2) is disposed between the cathode 1 and the anode 5, and these electrodes are crossed in a matrix to form a stripe shape. The signal voltage is applied in time series by the luminance signal circuit 34 and the control circuit 35 with a built-in shift register, and light is emitted at each of a large number of crossing positions (pixels).
[0025]
Therefore, with such a configuration, it can be used not only as a display but also as an image reproducing apparatus. Note that the above-described stripe pattern can be arranged for each color of R, G, and B, and can be configured for full color or multicolor.
[0026]
In a display device composed of a plurality of pixels using such an organic EL element, the organic thin film layers 2, 3, and 4 that emit light are generally sandwiched between the transparent electrode 5 and the metal electrode 1, and the transparent electrode 5 side Flashes on.
[0027]
[Problems to be solved by the invention]
However, the organic EL elements as described above still have unsolved problems.
[0028]
  The three primary colors of R, G, and B when applying organic EL elements to color displays(Especially B)Stable light emission is an indispensable condition. However, in the device fabrication process, when completely different material systems R, G, and B are used, the process is not complicated and takes time.
[0029]
An object of the present invention is to provide an electroluminescent element having an element structure that can be manufactured simply and at low cost and capable of stable light emission, and a method for manufacturing the same.
[0030]
[Means for Solving the Problems]
The present inventor has intensively studied the above situation, and found that a device can be easily and inexpensively manufactured by using a common material as much as possible in at least three kinds of laminated bodies having light emitting regions of respective colors. The invention has been reached.
[0031]
  That is, the present invention has at least three kinds of organic material laminates in which a hole transporting light emitting layer and an electron transporting light emitting layer are laminated, and these laminates are composed of a common material layer. An electroluminescent element having at least three emission colors, the electroluminescent light emitting layer comprising the common light emitting layer and the electron transporting light emitting layer made of a common material layer, wherein at least one of the laminated bodies, An insulating layer for separating the gaps is provided under the hole transporting light emitting layer.And
    Of the laminates, the first laminate includes the hole transporting light emitting layer and the electron transporting light emitting layer.  A hole blocking layer, and in the hole-transporting light-emitting layer, electron-hole recycling is performed.  Blue light emission due to bonding,
    The second stacked body of the stacked bodies has the electron transporting property in contact with the hole transporting light emitting layer.  In the light emitting layer, green light emission occurs due to electron-hole recombination,
    A third stacked body of the stacked bodies includes an electron transporting light emitting layer on the hole transporting light emitting layer.  Red light emission is generated by recombination of electrons and holes in the light emitting layer formed as a part
It is characterized byThe present invention relates to an electroluminescent element. In this electroluminescent device, the hole transporting light emitting layer is made of a hole transporting material for short wavelength light emission, and a hole blocking layer made of a phenanthroline derivative, for example, between the hole transporting light emitting layer and the electron transporting light emitting layer. In the hole transporting light emitting layer, blue light emission can be obtained by electron-hole recombination.
[0032]
  According to the electroluminescent device of the present invention, the hole transporting light emitting layer and the electron transporting light emitting layer are used as a common material layer between the respective laminates in which the hole transporting light emitting layer and the electron transporting light emitting layer are laminated. Therefore, it is possible to easily and cost-effectively produce a laminate that exhibits each color of light emission by a simple process. Further, by forming the common layers on the entire effective pixel area with a large aperture mask, the film forming property or the step coverage is improved, and the leakage current between the cathode and the anode can be reduced.
  In addition, the laminates are divided by insulating layers, and the first laminate of these laminates includes a hole block layer between the hole transporting light emitting layer and the electron transporting light emitting layer. Therefore, it is possible to effectively control the hole transport in the hole blocking layer so that electron-hole recombination is efficiently generated in the hole transporting light emitting layer. Light can be emitted to emit blue light. In the second and third laminates in which no hole blocking layer is present, green light emission due to electron-hole recombination and red light emission due to the red light emitting layer occur in the electron transporting light emitting layer, so that at least blue, green and It is possible to provide an electroluminescent element capable of supporting red full color light emission.
[0033]
  Further, the present invention provides a method for producing the electroluminescent device of the present invention with good reproducibility,
    At least three types of the laminates on a common substrateEach ofForming a first electrode of
    Forming an insulating layer separating the stacked bodies on the first electrode;
    On the first electrode, at least three kinds of the laminatesFormation areaForming a common hole-transporting light-emitting layer forming material in a region including, and forming each hole-transporting light-emitting layer for short wavelength light emission,
    In the formation region of the first laminate that emits blue light in the laminate, the holes  Forming a hole blocking layer on the transporting light emitting layer;
    A process for forming a red light emitting layer as a part of the electron transporting light emitting layer on the hole transporting light emitting layer.  About
    On the region including each of the hole transporting light emitting layers, at least three kinds of the laminatesForm of  Growth areaForming a common electron-transporting light-emitting layer forming material in a region including the material to form each electron-transporting light-emitting layer;
    Forming a second electrode of each of the at least three types of the stacked body on each of the electron-transporting light emitting layers so as to face the first electrode;
There is also provided a method for manufacturing an electroluminescent element having the following. In this manufacturing method, in at least one region of the laminate, the hole-transporting light-emitting layer is made of, for example, a phenanthroline derivative, and blue light emission is generated by electron-hole recombination in the hole-transporting light-emitting layer. Forming a hole blocking layerThis is very important.
[0034]
DETAILED DESCRIPTION OF THE INVENTION
  In the electroluminescent device and the method for producing the same according to the present invention, in at least one of the laminates, a hole transporting light emitting layer is formed so that blue light emission can be obtained by electron-hole recombination in the hole transporting light emitting layer. A hole blocking layer made of, for example, a phenanthroline derivative is formed between the electron transporting light emitting layer.
[0035]
  According to such an electroluminescent device, the hole transport property described above is used.Luminescent layerLight emission due to electron-hole recombination is obtained (ie, the hole transport layer also serves as a light-emitting layer that is an electron-hole recombination region). Light emission, particularly blue light emission.
[0036]
Therefore, an electroluminescent element (especially a low-voltage driven, self-luminous, thin amorphous organic electroluminescent element, which has been considered to be a difficult structure due to the absence of an electron transport material having excellent non-luminous properties until now. ), The hole transport layer can also serve as the light emitting layer, and can provide an electroluminescent device having a long-life element structure that provides stable light emission for a long time.
[0037]
That is, even in an organic electroluminescent device in which the hole transport layer is a light emitting layer, stable light emission with high luminance and high efficiency can be obtained. Particularly, blue light emission is remarkable, and is 10000 cd / m by DC driving.²As described above, the peak luminance of 55000 cd / m in terms of direct current is also obtained by pulse driving at a 1/100 duty ratio.²It is possible to obtain the above.
[0038]
In addition to blue light-emitting elements, green light emission, red light emission by doping, yellow light emission, and chromaticity adjustment by doping are also possible. As a result, it is possible to produce an organic electric field blue light-emitting element capable of obtaining blue light emission with excellent chromaticity with high luminance, possibility of material development and time reduction, and a new light-emitting material system and Design guidelines for electron transport materials can be provided.
[0039]
In the electroluminescent device and the method for manufacturing the same according to the present invention, it is preferable that the light emitting region is mainly an organic hole transport layer, and has a hole block layer for causing the recombination in the hole transport layer.
[0041]
  In the present inventionIn addition, the highest occupied molecular orbital level of the hole block layer is formed by contacting each organic layer stacked on both sides of the hole block layer (in particular, the hole transport layer).Sexual luminescenceLayer and said electron transportSexual luminescenceIt is desirable that it is below the highest occupied molecular orbital level of the lower energetically of the highest occupied molecular orbital level of each layer.
[0042]
  In addition, the lowest unoccupied molecular orbital level of the hole blocking layer is determined so that each organic layer stacked on both sides of the hole blocking layer (particularly the hole transport layer)Sexual luminescenceLayer and said electron transportSexual luminescenceIt is desirable that the energy level is not less than the lowest unoccupied molecular orbital level of the lower energy level among the lowest unoccupied molecular orbital levels of the layer) and lower than the lowest unoccupied molecular orbital level of the higher energy level.
[0043]
The hole blocking layer is preferably made of a non-light emitting material having a low fluorescence yield, and may have a multilayer structure.
[0044]
Furthermore, although the hole blocking layer is not limited in terms of material, in order to prevent the formation of exciplex (dimer) at the interface with the hole transporting light emitting layer (that is, decrease in luminous efficiency) A non-light emitting material with low fluorescence yield is preferred.
[0045]
  Said hoLight transport layerIs preferably made of a hole transporting material for short wavelength light emission. Further, as a material that can be used for the hole blocking layer, a phenanthroline derivative shown in FIG. 4 is suitable. Specifically, for example, structural formula 1 shown in FIG. 5, structural formula 2 shown in FIG. Structural formula 3 shown in FIG. 7, Structural formula 4 shown in FIG. 8, Structural formula 5 shown in FIG. 9, Structural formula 6 shown in FIG. 10, Structural formula 7 shown in FIG. 11, Structural formula 8 shown in FIG. Each material of structural formula 9 shown in FIG. 14 and structural formula 10 shown in FIG.
[0046]
  Also, the aboveDoes not have a hole blocking layerIn at least one of the laminates, the electron transport propertyLuminescent layerAmong them, it is desirable to obtain green light emission by electron-hole recombination.
[0047]
  Furthermore, theDoes not have a hole blocking layerIn at least one of the laminates, the electron transport propertyLuminescent layerAmong them, it is desirable to obtain red light emission by electron-hole recombination.
[0048]
As described above, an organic layer for obtaining blue light emission by electron-hole recombination in the light emitting region is laminated as a hole blocking layer, thereby providing a hole transporting light emitting layer that is stable, high brightness, and driven at a low voltage. An organic electroluminescence device can be obtained, and in the stacked region of the organic material without the hole blocking layer, red or green light emission can be obtained by electron-hole recombination in the electron transport layer, at least R, G, It is possible to provide an excellent organic electroluminescence device that can cope with B.
[0049]
In the above element, it is desirable that a transparent electrode, an organic layer (in particular, an organic hole transport layer, a hole block layer, an organic electron transport layer) and a metal electrode are sequentially laminated on an optically transparent substrate.
[0050]
In this case, it is preferable that the transparent electrode, the organic layer, and the metal electrode be configured as an organic electroluminescent element in which a matrix pattern is formed on the same substrate.
[0051]
Thereby, said element is comprised as a suitable organic electroluminescent element, and will also become a suitable thing as an element for color displays.
[0052]
Hereinafter, preferred embodiments of the present invention will be described.
[0053]
<First Embodiment>
FIG. 3 is a schematic cross-sectional view showing a main part of the organic EL element 21 according to the first embodiment of the present invention.
[0054]
The organic EL element 21 according to the present embodiment has an organic electroluminescent element portion 21B (blue), 21G (green), and 21R (red) made of a laminated body of amorphous organic thin films for at least three types of light emission. The glass substrate 6 is provided.
[0055]
In the blue light emitting element portion 21B shown in FIG. 3A, a transparent electrode 5 made of ITO (Indium Tin Oxide) or Zn-doped indium oxide or the like (hereinafter the same) is used as a row or line electrode on the glass substrate 6. It is formed by a method such as sputtering or vacuum vapor deposition, and a blue light emitting hole transport layer 4a, a hole transporting light emitting layer 4b, a hole blocking layer 33, an electron transporting layer (or an electron transporting light emitting layer) 2, A cathode electrode 1 as a column electrode is stacked by a vacuum deposition method.
[0056]
In the green light emitting element portion 21G shown in FIG. 3 (B), the transparent electrode 5 made of ITO (Indium Tin Oxide) or the like is formed on the glass substrate 6 by a method such as sputtering or vacuum vapor deposition, and the above-described ones are sequentially formed thereon. The hole transport layer 4a, the hole transport light emitting layer 4b, the electron transport layer 2 for green light emission, and the cathode electrode 1 as a column electrode are laminated by a vacuum deposition method, and the hole block layer is not provided.
[0057]
In the red light emitting element portion 21R shown in FIG. 3C, the transparent electrode 5 made of ITO (Indium Tin Oxide) or the like is formed on the glass substrate 6 by a method such as sputtering or vacuum deposition, and holes are sequentially formed thereon. A transport layer 4a, a hole transport light emitting layer 4b, an electron transport layer 32 for red light emission, an electron transport layer 2, and a cathode electrode 1 as a column electrode are laminated by a vacuum deposition method.
[0058]
The organic EL element 21 in FIG. 3 is characterized in that the transparent electrode 5 is used as a row electrode or a line electrode common to at least three kinds of light emitting element parts on the glass substrate 6 common to the light emitting element parts 21B, 21G, and 21R. And forming each hole transport layer 4a, 4b made of a common hole transport layer forming material on the region including each light emitting element part on the transparent electrode, and on the region including each hole transport layer, Each electron transport layer 2 made of a common electron transport forming material is formed on a region including each light emitting element part, and each cathode electrode 1 of each light emitting element part is formed on each of these electron transport layers as a transparent electrode. 5 in a matrix pattern. However, each light emitting element portion has a unique layer structure, and the blue light emitting element portion 21B has a hole block layer 33 and the red light emitting element portion 21R has a red light emitting layer 32 in a stripe pattern.
[0059]
Accordingly, in each light emitting element portion, the light emitting region is formed by forming the hole transport layer 4 (4a, 4b) and the electron transport layer 2 with a common material. Matrix) can be easily and inexpensively manufactured by a simple process. In addition, by forming the common layers with a large opening mask over the entire effective pixel region, the film forming property or the step coverage is improved, and the leakage current between the cathode and the anode can be reduced.
[0060]
The blue light emitting element portion 21B is configured as a structure in which the hole transport layer 4 has the performance as a light emitting layer, and the basic structure is the same in other embodiments described later.
[0061]
The element part 21B of the present embodiment is characterized in that the hole block layer 33 is inserted and laminated between the hole transport layer 4 and the electron transport layer 2, so that the electron − This is to promote recombination of holes and to obtain light emission in the hole transport layer 4.
[0062]
FIG. 15 schematically shows the laminated structure of the above-described embodiment (FIG. 3A) using a band model.
[0063]
In FIG. 15, a thick line (L) shown in the layer of cathode 1 and ITO transparent electrode 5 made of Al and Al—Li (aluminum-lithium)₁, L₂) Is an approximate work function of each metal, and in each layer between these two electrodes, an upper thick line l₁, L₂, L_Three, L_FourAnd the numbers indicate the level of the respective lowest unoccupied molecular orbital (LUMO), with the lower bold line l_Five, L₆, L₇, L₈And the numbers indicate the respective highest occupied molecular orbital (HOMO) levels. However, the energy level value in FIG. 15 is an example and varies depending on the material.
[0064]
In this organic EL element, as shown in FIG. 15, the holes h injected from the transparent electrode 5 serving as the anode move through the hole transport layer 4, while the electrons e injected from the metal electrode 1 serving as the cathode are transferred. The electron-hole moves through the electron transport layer 2 and recombines in the hole transporting light emitting layer 4 to emit light.
[0065]
Since the electrons e injected from the metal electrode 1 as the cathode have the property of moving to the lower energy level, the metal electrode 1, the electron transport layer 2, the hole blocking layer 33, the hole transporting light emitting layer 4b, the hole transport. Minimum unoccupied molecular orbital (LUMO) level l of each layer in order of layer 4a₁~ L_FourCan reach the hole transporting light emitting layers 4b and 4a.
[0066]
On the other hand, the hole h injected from the ITO transparent electrode 5 as the anode has a property of moving to a higher energy level. Therefore, the hole transport layer 4a, the hole transport light-emitting layer 4b, and the hole block layer 33 are sequentially formed. Maximum occupied molecular orbital (HOMO) level l_Five~ L₇It can move to the electron transport layer 2 via.
[0067]
However, as shown in FIG. 15, the highest occupied molecular orbital (HOMO) level l of the hole block layer 33₇Than the highest occupied molecular orbital (HOMO) level of the electron transport layer 2₈Since this is lower in energy, the injected hole h becomes difficult to move from the hole blocking layer 33 to the electron transporting layer 2 and fills the hole blocking layer 33.
[0068]
As a result, the hole h filled in the hole blocking layer 33 promotes electron-hole recombination in the hole transport layer 4 and causes the light emitting materials of the hole transporting light emitting layers 4a and 4b constituting the hole transport layer 4 to emit light. It will be.
[0069]
Thus, by providing the hole blocking layer 33, the hole blocking layer 33 effectively controls the transport of holes h so that electron-hole recombination occurs efficiently in the hole transporting layer 4. Then, among the hole transporting light emitting layers 4a and 4b that emit light, the light emission by the hole transporting light emitting layer 4a is added to the light emission mainly by the hole transporting light emitting layer 4b adjacent to the hole blocking layer 33, and the specific shape as shown in FIG. It emits light of wavelength (blue).
[0070]
Originally, electron injection from the cathode electrode 1 and hole injection from the anode electrode 5 cause electron-hole recombination in each of the electron transport layer 2 and the hole transport layer 4. Therefore, when the hole blocking layer 33 does not exist as described above, electron-hole recombination occurs at the interface between the electron transport layer 2 and the hole transport layer 4, and only light having a long wavelength can be obtained. However, by providing the hole blocking layer 33 as in this embodiment, blue light emission can be promoted by using the hole transport layer 4 containing the luminescent substance as the light emitting region.
[0071]
As described above, the hole blocking layer 33 is for controlling the transport of the holes h. For this purpose, the highest occupied molecular orbital (HOMO) of the hole blocking layer 33 is formed by the hole transporting light emitting layer 4b and the electrons. The highest occupied molecular orbital (HOMO) level of the transport layer 2 is below the highest occupied molecular orbital (HOMO) level of the lower energy level, and the lowest unoccupied molecular orbital (LUMO) of the hole blocking layer 33 is The lowest unoccupied molecular orbital (LUMO) level of the lowest unoccupied molecular orbital (LUMO) level of the hole transporting light-emitting layer 4b and the electron transporting layer 2 is higher than the lowest unoccupied molecular orbital (LUMO) level of the lower energy, and What is necessary is just to be below an occupied molecular orbital (LUMO) level, and it is not limited to said structure.
[0072]
The hole block layer 33 can be formed of various materials, and the thickness of the hole block layer 33 may be changed as long as the function can be maintained. The thickness is preferably 1 to 1000 mm (0.1 to 100 nm). However, if the thickness is too thin, the hole blocking ability is incomplete and the recombination region easily spans the hole transport layer and the electron transport layer. If it is too thick, light may not be emitted due to an increase in film resistance.
[0073]
In the green light emitting element portion 21G, since the hole block layer 33 is not provided, holes enter the electron transport layer 2 and electron-hole recombination occurs in the electron transport layer 2. The transport layer 2 emits light and emits light of a specific wavelength (green) as shown in FIG.
[0074]
In the red light emitting element portion 21R, since the red light emitting layer 32 is provided instead of the hole blocking layer 33, holes enter the light emitting layer 32 and electron-hole recombination occurs in the light emitting layer 32. Therefore, the light emitting layer 32 emits light and emits light having a specific wavelength (red) as shown in FIG.
[0075]
Said organic EL element 21 is produced using the vacuum evaporation apparatus 11 like FIG. Inside this apparatus, a pair of support means 13 fixed under the arm 12 is provided, and the mask 22 can be set between the both fixing means 13 and 13 with the transparent glass substrate 6 facing downward. A stage mechanism (not shown) is provided. The shutter 14 supported by the support shaft 14a is disposed below the glass substrate 6 and the mask 22, and a predetermined number of various vapor deposition sources 28 are disposed below the shutter 14. Each vapor deposition source is heated by a resistance heating method using a power source 29. For this heating, an EB (electron beam) heating method or the like is used as necessary.
[0076]
In the above apparatus, the mask 22 is for pixels, and the shutter 14 is for vapor deposition material. The shutter 14 is rotated about the support shaft 14a to block the vapor flow of the material in accordance with the sublimation temperature of the vapor deposition material.
[0077]
In practice, three types of masks 22 are used, as shown in FIG. After the hole transport layer 4 is formed in common on each element part through the large opening 23a using the mask 22a, the hole block layer 33 is formed on the blue light emitting element part through the slit-like opening 23b using the mask 22b. Then, a red light emitting layer 32 is formed in a predetermined pattern on the red light emitting element portion 21R through the slit-like opening 23c using a mask 22c, and then common to each element portion using the mask 22a. The electron transport layer 2 is formed through the large opening 23a, and the cathode electrode 1 is formed in a predetermined pattern on each element using a mask (not shown).
[0078]
In this way, as shown in FIG. 17, each light emitting element part 21B, 21G, 21R is formed in stripe form on the transparent electrode 5 on the common glass substrate 6, respectively. These stripes are divided into light emitting areas by an insulating layer (not shown here). Thus, when each light emitting element part is formed on the transparent electrode 5 in the same pattern, the carrier transport property between the cathode and the anode is improved, and the voltage drop between the two electrodes can be reduced.
[0079]
1 and 2 are diagrams showing a specific example of the organic EL element 21 produced by the vacuum vapor deposition apparatus. That is, after the ITO transparent electrode 5 to be a line electrode is deposited on the glass substrate 6 by the above-described vacuum deposition apparatus, it is SiO along the column direction₂24 is deposited in a predetermined pattern, and this SiO 2₂In the meantime, the transparent electrodes 5 are respectively exposed to the pixel pattern. Next, each of the organic layers 4a, 4b, 33, 32, and 2 and a metal electrode 1 (for example, a laminate of the LiF layer 1a and the Al layer 1b) are sequentially formed in a stripe pattern in the column direction using a vapor deposition mask. A matrix is produced. The above-described vapor deposition masks 22a, 22b, and 22c are used for forming the organic layers 4, 2, 33, and 32. The organic layers 33 and 32 are formed on the transparent electrode 5 in the line direction, but may be formed in the column direction orthogonal to the transparent electrode 5.
[0080]
According to this organic EL element 21, in each light emitting element part, the light emitting region exists independently in the hole transport layer 4 (4a, 4b) and the electron transport layer 2 (32), and there is a hole between each light emitting element part. Since the transport layer 4 (4a, 4b) and the electron transport layer 2 are each formed of a common material layer, a stripe-shaped laminate (matrix) exhibiting each color emission color can be easily and inexpensively by a simple process. It can be produced. In addition, since the organic layers 4a, 4b, and 2 are formed in a large area, the film forming property including the insulating layer 24 is improved, the leakage current between the cathode and the anode is small, and the stable and reliable performance. Can be obtained. As shown by a broken line in FIG. 1B, this effect is further improved if the upper surface of the insulating layer 24 is curved.
[0081]
In the vacuum deposition apparatus 11 described above, in addition to those having the pixels as shown in FIGS. 1 and 2, the shape and size can be changed. It can also be formed.
[0082]
The transparent electrode, organic hole transporting layer, organic hole blocking layer, red light emitting layer, organic electron transporting layer, and metal electrode of the electroluminescent element may each have a laminated structure composed of a plurality of layers.
[0083]
Further, each organic layer in the electroluminescent element may be formed by other film forming methods involving sublimation or vaporization, or methods such as spin coating and casting, in addition to vacuum deposition.
[0084]
In addition, the hole transporting light emitting layer of the above electroluminescent device may be subjected to co-evaporation of trace molecules for controlling the emission spectrum of the device, and includes a small amount of organic substances such as perylene derivatives and coumarin derivatives. An organic thin film may be sufficient.
[0085]
The electroluminescent element is suitable for light emission of three colors of R, G, and B, but other luminescent colors can be obtained depending on the type of luminescent material used.
[0086]
Examples of materials that can be used as hole transport materials include benzidine or its derivatives, styrylamine or its derivatives, triphenylmethane or its derivatives, porphyrin or its derivatives, triazole or its derivatives, imidazole or its derivatives, oxadi Azole or derivative thereof, polyarylalkane or derivative thereof, phenylenediamine or derivative thereof, arylamine or derivative thereof, oxazole or derivative thereof, anthracene or derivative thereof, fluorenone or derivative thereof, hydrazone or derivative thereof, stilbene or derivative thereof, or Examples include heterocyclic conjugated monomers, oligomers, polymers and the like such as polysilane compounds, vinylcarbazole compounds, thiophene compounds, and aniline compounds.
[0087]
Specifically, α-naphthylphenyldiamine, porphyrin, metal tetraphenylporphyrin, metal naphthalocyanine, 4,4 ′, 4 ″ -trimethyltriphenylamine, 4,4 ′, 4 ″ -tris (3-methylphenylphenyl Amino) triphenylamine, N, N, N ′, N′-tetrakis (p-tolyl) p-phenylenediamine, N, N, N ′, N′-tetraphenyl-4,4′-diaminobiphenyl, N— Examples include, but are not limited to, phenylcarbazole, 4-di-p-tolylaminostilbene, poly (paraphenylene vinylene), poly (thiophene vinylene), poly (2,2′-thienylpyrrole), and the like. .
[0088]
Examples of materials that can be used as the electron transporting material include quinoline or a derivative thereof, perylene or a derivative thereof, bisstyryl or a derivative thereof, pyrazine or a derivative thereof.
[0089]
Specific examples include 8-hydroxyquinoline aluminum, anthracene, naphthalene, phenanthrene, pyrene, chrysene, perylene, butadiene, coumarin, acridine, stilbene, and derivatives thereof.
[0090]
In addition to BSB-BCN, examples of the red light emitting material include those obtained by doping the electron transport material with DCM, DCM2, Nile Red, phenoxazine, or the like.
[0091]
There are no restrictions on the materials used for the anode electrode and cathode electrode of the electroluminescent element.
[0092]
For the cathode electrode material, in order to inject electrons efficiently, it is preferable to use a metal having a small work function from the vacuum level of the electrode material. In addition to the aluminum-lithium alloy, for example, aluminum, indium, magnesium, A low work function metal such as silver, calcium, barium, or lithium may be used alone or as an alloy with another metal with increased stability.
[0093]
In addition, in order to take out organic electroluminescence from the anode electrode side, ITO, which is a transparent electrode, was used for the anode electrode described later. However, in order to inject holes efficiently, the anode electrode material from the vacuum level was used. An electrode having a high work function, for example, gold, a tin dioxide-antimony mixture, or a zinc oxide-aluminum mixture may be used.
[0094]
In addition, by selecting a light emitting material, an organic electroluminescent element for full color or multicolor that emits three colors of R, G, and B can be manufactured. In addition, the present invention can be applied to an organic electroluminescent element that can be used not only for a display but also for a light source, and can also be applied to other optical uses.
[0095]
The organic electroluminescent device described above may be sealed with germanium oxide or the like in order to enhance stability to eliminate the influence of oxygen in the atmosphere, and the device is driven in a vacuum state. May be.
[0096]
<Second Embodiment>
FIG. 24 is a schematic cross-sectional view showing the main part of the blue light emitting element portion 21B according to the second embodiment of the present invention.
[0097]
In the organic EL device according to the present embodiment, the hole transporting light emitting layer 4b is formed on the ITO transparent electrode 5 and the hole transporting light emitting layer is formed as a single layer, as compared with the device of FIG. Is different. The other green light emitting element portion 21G and red light emitting element portion 21R are the same as the elements in FIG.
[0098]
<Third Embodiment>
FIG. 25 is a schematic cross-sectional view showing the main part of the blue light emitting element portion 21B according to the third embodiment of the present invention.
[0099]
In the organic EL device according to the present embodiment, a hole transport layer (also serving as a hole transport light-emitting layer) 4a is formed on the ITO transparent electrode 5 as compared with the device of FIG. 3, and the second embodiment described above. The hole transporting light emitting layer is formed as a single layer in the same manner as in FIG. Other than that, the second embodiment is the same as the second embodiment.
[0100]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples.
[0101]
Example 1
A specific configuration of the organic EL element 21 according to the present embodiment will be described based on a manufacturing method thereof.
[0102]
First, in order to fabricate a simple matrix of 30 mm × 36 mm and 12 sets of R, G, B stripes, an ITO transparent electrode 5 having a thickness of, for example, about 100 nm is formed on a 53 mm × 53 mm glass substrate 6 with a width of 1.15 mm and a spacing of 0. 36 pieces are formed at 1 mm, and the column side is made of SiO₂Thus, 31 insulating layers 24 with a width of 0.5 mm and an interval of 1.0 mm were formed. Therefore, the light emitting area of one organic electroluminescent element production cell was 1.0 mm × 1.15 mm, and the aperture ratio was 60.8%.
[0103]
Then, on the ITO transparent electrode 5, a mask 22 a having an opening 23 a of 40.0 mm × 48.0 mm is used, and m-MTDATA (4, 4 ′) is formed as a hole transport layer 4 a on the whole including the ITO electrode 5. , 4 "-tris (3-methylphenylphenylamino) triphenylamine: having the structural formula of FIG. 18 was deposited to a thickness of 30 nm under vacuum by a vacuum deposition method at a deposition rate of 0.2 to 0.4 nm / sec.
[0104]
Next, on the hole transport layer 4a, as the hole transport light emitting layer 4b, α-NPD (α-naphtylphenyldiamine: the structural formula of FIG. 19; this is α-PPD of FIG. 20A or FIG. B) α-TPD or TPD of FIG. 20 (C) may be vacuum-deposited (deposition rate 0.2 to 0.4 nm / sec) to a thickness of 50 nm to form a luminescent two-layer structure. A hole transport layer 4 was formed.
[0105]
Next, on the hole transport layer 4, the mask 22 b having 12 stripe-shaped openings 23 b having an area of 1.16 mm × 49 mm is replaced with a mask 22 b having a light emitting area of the ITO electrode 5 of 1.15 mm × 48.0 mm. A phenanthroline derivative represented by the general formula shown in FIG. 4, such as bathocuproine (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline: represented by the structural formula 2 in FIG. 6) As a hole blocking layer 33, vacuum deposition was performed on the transparent electrode 5 to a thickness of 20 nm (deposition rate: 0.2 to 0.4 nm / sec).
[0106]
Next, on the hole transport layer 4, the mask 22 c having 12 stripe-shaped openings 23 c having an area of 1.16 mm × 49 mm is replaced with a mask 22 c having 1.15 mm × 48.0 mm, which is the light emitting region of the ITO electrode 5. In the stripe pattern, BSB-BCN (shown by the structural formula of FIG. 23) is used as the electron-transporting red light emitting material layer 32, and the thickness is 20 nm on the transparent electrode 5 (deposition rate: 0.2 to 0.4 nm / sec). Was vacuum evaporated.
[0107]
Thereafter, the mask opening 23a is replaced with a mask 22a having an area of 40.0 mm × 48.00 mm, and Alq is used as the electron transport layer or the electron transport light emitting layer 2._Three(8-hydroxy quinoline aluminum: structural formula of FIG. 21) was vacuum-deposited to a thickness of 40 nm.
[0108]
Next, the area of the opening is replaced with a mask having a size of 1.16 mm × 49 mm, and Al—Li (aluminum-lithium alloy: Li concentration of about 1 mol%) is used as the cathode electrode 1 to a thickness of about 0.5 nm, and Al is further added. The organic EL element 21 corresponding to R, G, and B shown in FIG. 1 was produced by vacuum deposition to a thickness of about 200 nm.
[0109]
Next, the characteristics of the organic EL device according to this example are measured and the results are shown.
[0110]
FIG. 26 is a graph showing the spectral characteristics of the organic EL element 21 according to Example 1 shown in FIG. That is, in the light emitting region having bathocuproine functioning as a hole blocking layer, the maximum light emission wavelength was 460 nm, the coordinates on the CIE chromaticity coordinates were (0.155, 0.11), and good blue light emission was exhibited. It was clear from the shape of the emission spectrum that this was emission from α-NPD. In addition, the light emitting site without bathocuproine is Alq which is an electron transporting light emitting material._ThreeThe green light emission with the maximum light emission wavelength of 520 nm and CIE (0.33, 0.55) was obtained. α-NPD and Alq_ThreeThe portion of the stripe where BSB-BCN was vapor-deposited between them could obtain good red light emission with a maximum light emission wavelength of 635 nm and CIE (0.60, 0.39).
[0111]
As shown in FIG. 27, the luminance is such that the current density is 500 mA / cm in the blue light emitting region.²10,000 cd / m²And a current density of 1 mA / cm² The luminous efficiency at that time was 1.2 lm / W. In the green light emitting part, the current density is 100 mA / cm.²7000 cd / m²The current density is 1 mA / cm² The luminous efficiency at that time was 1.1 lm / W. In the red light emitting region, the current density is 500 mA / cm.²5600 cd / m²The current density is 1 mA / cm² The luminous efficiency at that time was 0.03 lm / W.
[0112]
Further, when this organic EL element is pulse-driven with a duty ratio of 1/100, the current density is 5500 mA / cm.²When converted to DC drive, the peak brightness is 55000cd / m²Thus, a high-performance and high-brightness blue light-emitting element portion that can sufficiently withstand practical use could be produced.
[0113]
Example 2
A specific configuration of the organic EL element 21 according to the present embodiment will be described based on a manufacturing method thereof.
[0114]
First, in order to fabricate a simple matrix of 30 mm × 36 mm and 12 sets of R, G, B stripes, an ITO transparent electrode 5 having a thickness of, for example, about 100 nm is formed on a 53 mm × 53 mm glass substrate 6 with a width of 1.15 mm and a spacing of 0. 36 pieces are formed at 1 mm, and the column side is made of SiO₂Thus, 31 insulating layers 24 with a width of 0.5 mm and an interval of 1.0 mm were formed. Therefore, the light emitting area of one organic electroluminescent element production cell was 1.0 mm × 1.15 mm, and the aperture ratio was 60.8%.
[0115]
Then, on the ITO transparent electrode 5, a mask 22 a having an opening 23 a of 40.0 mm × 48.0 mm is used, and m-MTDATA (4, 4 ′) is formed as a hole transport layer 4 a on the whole including the ITO electrode 5. , 4 "-tris (3-methylphenylphenylamino) triphenylamine: having the structural formula of FIG. 18 was deposited to a thickness of 30 nm under vacuum by a vacuum deposition method at a deposition rate of 0.2 to 0.4 nm / sec.
[0116]
Next, on the hole transport layer 4a, as the hole transport light emitting layer 4b, α-NPD (α-naphtylphenyldiamine: the structural formula of FIG. 19; this is α-PPD of FIG. 20A or FIG. B) α-TPD or TPD of FIG. 20 (C) may be vacuum-deposited (deposition rate 0.2 to 0.4 nm / sec) to a thickness of 50 nm to form a luminescent two-layer structure. A hole transport layer 4 was formed.
[0117]
Next, on the hole transport layer 4, the mask 22 b having 12 stripe-shaped openings 23 b having an area of 1.16 mm × 49 mm is replaced with a mask 22 b having a light emitting area of the ITO electrode 5 of 1.15 mm × 48.0 mm. A phenanthroline derivative represented by the general formula shown in FIG. 4, such as bathocuproine (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline: represented by the structural formula 2 in FIG. 6) As a hole blocking layer 33, vacuum deposition was performed on the transparent electrode 5 to a thickness of 20 nm (deposition rate: 0.2 to 0.4 nm / sec).
[0118]
Next, on the hole transport layer 4, the mask 22 c having 12 stripe-shaped openings 23 c having an area of 1.16 mm × 49 mm is replaced with a mask 22 c having 1.15 mm × 48.0 mm, which is the light emitting region of the ITO electrode 5. In the stripe pattern, DCM2 (shown by the structural formula of FIG. 22) and Alq_Three(8-hydroxy quinoline aliminum: structural formula of FIG. 21) and 20 nm on the transparent electrode 5 as the electron transporting red light emitting material layer 32 so that the molar ratio of DCM2 is 0.5 to 1%. Co-deposition was performed at a thickness (deposition rate of 0.2 to 0.4 nm / sec).
[0119]
Thereafter, the mask opening 23a is replaced with a mask 22a having an area of 40.0 mm × 48.00 mm, and Alq is used as the electron transport layer or the electron transport light emitting layer 2._Three(8-hydroxy quinoline aluminum: structural formula of FIG. 21) was vacuum-deposited to a thickness of 40 nm.
[0120]
Next, the area of the opening is replaced with a mask having a size of 1.16 mm × 49 mm, and Al—Li (aluminum-lithium alloy: Li concentration of about 1 mol%) is used as the cathode electrode 1 to a thickness of about 0.5 nm, and Al is further added. The organic EL element 21 corresponding to R, G, and B shown in FIG. 1 was produced by vacuum deposition to a thickness of about 200 nm.
[0121]
Next, the characteristics of the organic EL device according to this example are measured and the results are shown.
[0122]
That is, like the organic EL element 21 according to Example 1, in the light emitting region having bathocuproine functioning as a hole blocking layer, the maximum light emission wavelength is 460 nm, and the coordinates on the CIE chromaticity coordinates are (0.155, 0.11). There was good blue light emission. It was clear from the shape of the emission spectrum that this was emission from α-NPD. In addition, the light emitting site without bathocuproine is Alq which is an electron transporting light emitting material_ThreeThe green light emission with the maximum light emission wavelength of 520 nm and CIE (0.33, 0.55) was obtained. α-NPD and Alq_ThreeBetween DCM2 and Alq_ThreeThe portion of the stripe co-deposited with was able to obtain good red emission with a maximum emission wavelength of 645 nm and CIE (0.66, 0.34).
[0123]
The luminance is a current density of 500 mA / cm in the blue light emitting region.²10,000 cd / m²And a current density of 1 mA / cm² The luminous efficiency at that time was 1.2 lm / W. In the green light emitting part, the current density is 100 mA / cm.²7000 cd / m²The current density is 1 mA / cm² The luminous efficiency at that time was 1.1 lm / W. In the red light emitting region, the current density is 250 mA / cm.²160 cd / m²The current density is 1 mA / cm² The luminous efficiency at that time was 0.04 lm / W.
[0124]
Example 3
An organic EL device according to a third embodiment of the present invention will be described based on its manufacturing method.
[0125]
In the organic EL device according to the present example, the hole transport layer 4a is not provided, and the hole transporting light emitting layer 4b is α-NPD (α-naphtyl phenyl diamine: the structural formula of FIG. 19. This is shown in FIG. The α-PPD of FIG. 20 or the α-TPD of FIG. 20B or the TPD of (C) may be deposited by vacuum deposition to a thickness of, for example, 50 nm (deposition rate: 0.2 to 0.4 nm / sec). This is the same as the first embodiment except that the hole transporting light emitting layer is formed as a single layer.
[0126]
FIG. 28 is a graph showing the spectral characteristics of the organic EL device according to Example 3 shown in FIG.
[0127]
In the case of this example, the maximum emission wavelength (absorption peak) was about 460 nm, and the coordinates on the CIE chromaticity coordinates were (0.155, 0.11), and good blue emission was exhibited. About green light emission and red light emission, it was the same as that of FIG.
[0128]
As shown in FIG. 29, the current density is 400 mA / cm.²The brightness at 1400cd / m²Met.
[0129]
From the shape of the emission spectrum, it was clear that light was emitted from the hole transporting light emitting layer 4b made of α-NPD at the blue light emitting portion.
[0130]
In addition, as shown in the threshold voltage characteristics of FIG. 30, almost no current flows until the voltage reaches about 5V, and gradually begins to flow past 5V, and then quickly flows out from over 6V. That is, it indicates that low voltage driving is possible and that the threshold voltage characteristics are good.
[0131]
Example 4
An organic EL device according to a fourth embodiment of the present invention will be described based on its manufacturing method.
[0132]
In the organic EL device according to this example, m-MTDATA (4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine: having the structural formula of FIG. 18) is used as the hole transporting light emitting layer 4a by vacuum deposition. Evaporation was performed under a vacuum to a thickness of 50 nm (deposition rate: 0.2 to 0.4 nm / sec), and the hole transporting light emitting layer was formed as a single layer in the same manner as in the third example.
[0133]
FIG. 31 is a graph showing the spectral characteristics of the organic EL element according to Example 4 shown in FIG.
[0134]
In the case of this example, the maximum emission wavelength (absorption peak) was about 500 nm, and the coordinates on the CIE chromaticity coordinates were (0.26, 0.47), and good green emission was exhibited. About red light emission, it was the same as that of FIG.
[0135]
As shown in FIG. 32, the current density is 110 mA / cm at the blue light emitting region.²The brightness at 280cd / m²Met.
[0136]
From the shape of the emission spectrum, it was clear that the emission was from the hole transporting light emitting layer 4a made of m-MTDATA.
[0137]
From the voltage: brightness characteristics shown in FIG. 33, driving at a low voltage is possible and the luminance is good.
[0138]
As is apparent from the above description, in each of the organic EL elements of Examples 1 to 4 according to the present invention, the hole blocking layer 33 is provided between the hole transporting light emitting material 4a and / or 4b and the electron transporting layer 2. As a result, electron-hole recombination in the hole transport layer is sufficient, and it can also serve as the light emitting layer, and stable and efficient light emission can be obtained.
[0139]
Further, not only blue light emission as in Examples 1 and 2, but also green light emission as shown in Example 4, red light emission by doping, and chromaticity adjustment by doping were possible.
[0140]
Each example described above shows that it is possible to produce an organic EL element that can obtain blue light emission with excellent luminance even at high brightness even when using an existing material. It is considered that the time can be shortened and design guidelines for new light emitting material systems and electron transport materials can be shown.
[0141]
[Effects of the invention]
  As described above, the present inventionSexual luminescenceLayer and electron transportSexual luminescencelayerAnd are stackedHole transport between each laminateSexual luminescenceLayer and electron transportSexual luminescenceSince the layers are each formed of a common material layer, a laminated body exhibiting each luminescent color can be easily and inexpensively manufactured by a simple process. Further, by forming the common layers on the entire surface of the organic pixel region with a large opening mask, the film forming property or the step coverage is improved, and the leakage current between the cathode and the anode can be reduced.
[0142]
  In particular, light emission by electron-hole recombination can be obtained in a hole transporting organic material (for example, a hole blocking layer made of a phenanthroline derivative, a hole transporting light emitting layer, an electron transporting light emitting layer, and In the organic electroluminescence device in which the hole transport layer is a light-emitting layer, which has been conventionally considered to be a difficult structure due to the absence of an electron transport material having excellent non-light-emitting properties due to the structure inserted between Stable light emission with high luminance and high efficiency can be obtained. In particular, blue light emission is remarkable, and is 10000 cd / m with DC drive.²As described above, the peak luminance of 55000 cd / m in terms of direct current is also obtained by pulse driving at a 1/100 duty ratio.²It is possible to obtain the above.
  In the second and third laminates in which no hole blocking layer is present, green light emission due to electron-hole recombination and red light emission due to the red light emitting layer occur in the electron transporting light emitting layer, so that at least blue, green and It is possible to provide an electroluminescent element capable of supporting red full color light emission.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view (A) orthogonal to an anode of a main part of an organic EL element according to an embodiment of the present invention, and a cross-sectional view along the anode (B) (cross-sectional view along (B)-(B) in (A). ).
FIG. 2 is a schematic exploded perspective view of the organic EL element.
3A and 3B are schematic cross-sectional views of the main part of the organic EL element according to the first embodiment of the present invention, in which FIG. 3A is a blue light-emitting element part, FIG. 3B is a green light-emitting element part, and FIG. It is a red light emitting element part.
FIG. 4 is a diagram showing a general formula of a phenanthroline derivative that can be used for the hole blocking layer.
FIG. 5 is a diagram showing the structural formula 1 of the phenanthroline derivative.
FIG. 6 is a diagram showing the structural formula 2 of the phenanthroline derivative.
FIG. 7 is a diagram showing the structural formula 3 of the phenanthroline derivative.
FIG. 8 shows the structural formula 4 of the phenanthroline derivative.
FIG. 9 is a diagram showing the structural formula 5 of the phenanthroline derivative.
FIG. 10 is a diagram showing the structural formula 6 of the phenanthroline derivative.
FIG. 11 shows the structural formula 7 of the phenanthroline derivative.
FIG. 12 is a diagram showing the structural formula 8 of the phenanthroline derivative.
FIG. 13 is a diagram showing the structural formula 9 of the phenanthroline derivative.
FIG. 14 is a diagram showing the structural formula 10 of the phenanthroline derivative.
FIG. 15 is a band model diagram schematically showing a laminated structure of organic EL elements according to the embodiment.
FIG. 16 is a schematic cross-sectional view of a vacuum vapor deposition apparatus used in the embodiment.
FIG. 17 is a schematic plan view of the vapor deposition mask used in the embodiment and the produced organic EL element.
FIG. 18 is a diagram showing a structural formula of m-MTDATA (hole transporting light-emitting material) used in the embodiment.
FIG. 19 is a diagram showing a structural formula of α-NPD (hole transporting light-emitting material) used in the embodiment.
FIG. 20 shows another hole-transporting light-emitting material that can be used in the embodiment, in which (A) is the structural formula of α-PPD, (B) is the structural formula of α-TPD, and (C) is the TPD. It is a figure which shows these structural formulas.
FIG. 21 shows Alq used in the embodiment._ThreeIt is a figure which shows the structural formula of (electron transport material).
FIG. 22 is a diagram showing a structural formula of DCM2 (electron transporting light-emitting material) used in Examples of the present invention.
FIG. 23 is a diagram showing a structural formula of BSB-BCN (electron transporting light-emitting material) used in another example of the present invention.
FIG. 24 is a schematic cross-sectional view of a substantial part of an organic EL element according to a second embodiment of the present invention.
FIG. 25 is a schematic cross-sectional view of a main part of an organic EL element according to a third embodiment of the invention.
FIG. 26 is a graph showing the spectral characteristics of the organic EL device according to the first example of the invention.
FIG. 27 is a graph showing current-luminance characteristics of the organic EL element according to the first example.
FIG. 28 is a graph showing spectral characteristics of an organic EL device according to another example of the present invention.
FIG. 29 is a graph showing current-luminance characteristics of organic EL elements according to other examples.
FIG. 30 is a graph showing voltage-luminance characteristics of organic EL elements according to other examples.
FIG. 31 is a graph showing the spectral characteristics of an organic EL device according to another example of the present invention.
FIG. 32 is a graph showing current-luminance characteristics of organic EL elements according to other examples.
FIG. 33 is a graph showing voltage-luminance characteristics of organic EL elements according to other examples.
FIG. 34 is a schematic cross-sectional view showing an example of a conventional organic EL element.
FIG. 35 is a schematic cross-sectional view showing an example of the other organic EL element.
FIG. 36 is a schematic perspective view showing a specific example of the organic EL element.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Metal electrode (cathode), 2 ... Electron transport layer, 4 ... Hole transport layer,
4a, 4b ... hole transporting light emitting layer, 5 ... ITO transparent electrode (anode),
6 ... Glass substrate, 10, 20, 21 ... Organic EL element,
21R ... Red light emitting element part, 21G ... Green light emitting element part,
21B ... Blue light emitting element part, 22, 22a, 22b, 22c ... Evaporation mask,
24 ... insulating layer, 32 ... red light emitting layer, 33 ... hole blocking layer,
e ... Electronic, h ... Hall

Claims (2)

It has at least three kinds of organic material laminates in which a hole transporting light emitting layer and an electron transporting light emitting layer are laminated, and these laminates are common to the hole transporting light emitting layer made of a common material layer. An electroluminescent element having at least three emission colors, wherein the insulating layer separates between the stacked bodies in at least one of the stacked bodies. Is provided under the hole transporting light emitting layer ,
The first stacked body of the stacked bodies includes a hole blocking layer between the hole transporting light emitting layer and the electron transporting light emitting layer, and blue color due to electron-hole recombination in the hole transporting light emitting layer. Causing luminescence,
The second stacked body among the stacked bodies generates green light emission by electron-hole recombination in the electron transporting light emitting layer in contact with the hole transporting light emitting layer ,
The third stacked body among the stacked bodies emits red light by electron-hole recombination in a light emitting layer formed as a part of the electron transporting light emitting layer on the hole transporting light emitting layer.
An electroluminescent element characterized by the above . It has at least three kinds of organic material laminates in which a hole transporting light emitting layer and an electron transporting light emitting layer are laminated, and these laminates are common to the hole transporting light emitting layer made of a common material layer. A method for producing an electroluminescent element having at least three luminescent colors, comprising the electron-transporting luminescent layer comprising a material layer,
Forming a first electrode of each of at least three types of the laminate on a common substrate;
Forming an insulating layer separating the stacked bodies on the first electrode;
Forming a hole transporting light emitting layer forming material common to a region including the formation region of at least three types of the stacked body on the first electrode to form each hole transporting light emitting layer for short wavelength light emission; When,
Forming a hole blocking layer on each of the hole transporting light emitting layers in the formation region of the first stacked body that emits blue light in the stacked body; and
And a red light-emitting layer as engineering formed as part of the electron transport light-emitting layer to the hole transporting light-emitting layer,
On a region including the respective hole transporting light-emitting layer, forming a by forming a common electron transport light-emitting layer forming material in a region including a shape forming region of the at least three of said laminate each electron transport light-emitting layer And a process of
Forming a second electrode of each of the at least three types of the stacked body on each of the electron-transporting light-emitting layers so as to face the first electrode.

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