CN108470839B - Top-emitting OLED device with improved visual angle characteristic - Google Patents

Top-emitting OLED device with improved visual angle characteristic Download PDF

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CN108470839B
CN108470839B CN201810315666.4A CN201810315666A CN108470839B CN 108470839 B CN108470839 B CN 108470839B CN 201810315666 A CN201810315666 A CN 201810315666A CN 108470839 B CN108470839 B CN 108470839B
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hole injection
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李维维
刘嵩
何麟
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Beijing Visionox Technology Co Ltd
Kunshan New Flat Panel Display Technology Center Co Ltd
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Beijing Visionox Technology Co Ltd
Kunshan New Flat Panel Display Technology Center Co Ltd
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/80Constructional details
    • H10K50/85Arrangements for extracting light from the devices
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17Carrier injection layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/631Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine

Abstract

The invention discloses a top-emitting OLED device with improved viewing angle characteristics. The structure comprises a substrate, a first electrode, a hole injection layer, a hole transport layer, a luminescent layer, an electron transport layer, a second electrode and a light output coupling layer; according to the invention, the condition of enhancing the interference between the reflected light of the first electrode and the emitted light of the light-emitting layer is destroyed by increasing the refractive index of the hole injection layer, so that the wide-angle interference in the OLED device is weakened, and the microcavity effect is inhibited. Meanwhile, the ultra-thin second electrode structure is matched, and the light output coupling layer is used for assisting, so that the transmissivity and the light guide rate of light emitted by the light emitting layer are improved. The technical problem that the luminous property is reduced along with the deviation of the visual angle in the top-emitting OLED can be solved by the scheme of the invention, and the top-emitting OLED is particularly suitable for the field of flat panel display.

Description

Top-emitting OLED device with improved visual angle characteristic
The invention relates to a divisional application, wherein the original application number is 201310752797.6, the application date is 2013, 12 and 31, and the invention name is: a top-emitting OLED device with improved viewing angle characteristics.
Technical Field
The invention relates to the field of organic electroluminescent devices, in particular to a top-emitting OLED device with improved visual angle characteristics.
Background
Organic Light Emitting diodes (OLEDs for short) are used as novel active Light Emitting display devices, which are Light in weight, thin in thickness, and highly resistant to shock, and meanwhile, use Organic semiconductors to emit Light, have a wide material selection range, can realize full color display in a visible Light range, and are easy to realize white Light illumination. Compared with the existing mainstream Liquid Crystal Display (LCD for short), the Liquid Crystal Display has the advantages of wider viewing angle, faster response speed, no need of backlight illumination, high luminous efficiency, and capability of realizing flexible Display, and is a Display device with the greatest potential to replace the LCD.
The OLED device can be divided into a Bottom Emitting OLED (Bottom Emitting OLED, abbreviated as BEOLED) and a Top Emitting OLED (Top Emitting OLED, abbreviated as TEOLED) according to the light Emitting position. In the BEOLED, an OLED is fabricated on a glass substrate covered with a transparent Indium Tin Oxide (ITO) or Indium Zinc Oxide (IZO) electrode, and when a voltage is applied to the OLED, light emitted from the OLED is emitted from the bottom through the transparent ITO (or IZO) electrode and the glass substrate. In the BEOLED structure, a transparent ITO (or IZO) electrode is connected to a Thin Film Transistor (TFT) for driving the OLED, and there is a problem that the light emitting area of the OLED competes with the TFT, resulting in a low Aperture Ratio (Aperture Ratio) of the device. The top-emission OLED is manufactured by covering an opaque total reflection electrode on a glass or silicon substrate, and when voltage is applied to the OLED, light is emitted from a transparent or semitransparent cathode on the top. In the display based on the top-emitting OLED device, the TFT for driving the OLED is manufactured below the OLED, and the light-emitting surface is separated from the TFT, so that the problem of low aperture ratio can be fundamentally solved.
The top-emitting OLED comprises a total reflection electrode and a semitransparent electrode, the structure can form a microcavity effect, strong multi-beam interference is generated by the microcavity effect, the microcavity effect has the functions of selecting, narrowing, enhancing and the like on a light source, the microcavity effect is often used for improving the chromaticity of a device, enhancing the emission intensity of a specific wavelength, changing the light emitting color of the device and the like, but the microcavity effect influences the visual angle characteristics of the device, namely, the light emitting peak shifts along with the shift of the visual angle, so that the problems of the difference of the display brightness, the shift of the chromaticity and the like are caused.
At present, a scheme for improving the viewing angle characteristic of a top-emission OLED generally includes adding a light output coupling layer on a cathode, for example, an organic substance with high refractive index and low absorption rate such as 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP for short), or evaporating a layer of high refractive index dielectric ZnSe, ZnS, etc. on the surface of a semitransparent cathode as a coupling layer, so as to improve the transmittance and light guide efficiency, and further reduce the influence of multi-beam interference.
Disclosure of Invention
Therefore, the present invention is directed to improve the deviation of luminance and chromaticity with the viewing angle in a top-emitting OLED device, thereby providing a top-emitting OLED device with improved viewing angle characteristics.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the invention provides a top-emitting OLED device with improved visual angle characteristics, which comprises a substrate, and a first electrode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, a second electrode and a light output coupling layer which are arranged on the substrate in a superposed manner; the light transmittance of the second electrode is not less than 25%, and the refractive index of the hole injection layer is not less than 1.8;
when the light-emitting wavelength of the light-emitting layer is in a green light band, the refractive index N of the hole injection layer is more than or equal to 1.9.
In the above top-emitting OLED device for improving the viewing angle characteristic, the second electrode is indium tin oxide or indium zinc oxide or metallic silver.
In the above top-emitting OLED device with improved viewing angle characteristics, the second electrode includes a first metal layer and a second metal layer, wherein the first metal layer is an alkali metal or an alloy thereof, an alkaline earth metal or an alloy thereof, and the second metal layer is metallic silver.
In the above top-emitting OLED device with improved viewing angle characteristics, the thickness of the second electrode is 10nm to 30 nm.
According to the top-emitting OLED device with the improved visual angle characteristic, when the light-emitting wavelength of the light-emitting layer is in a blue light wave band, the refractive index N of the hole injection layer is larger than or equal to 2.0.
According to the top-emitting OLED device with the improved visual angle characteristic, when the light-emitting wavelength of the light-emitting layer is in a red light wave band, the refractive index N of the hole injection layer is larger than or equal to 1.8.
In the above top-emitting OLED device with improved viewing angle characteristics, the structural formula of the material of the hole injection layer is:
Figure BDA0001623684760000031
Figure BDA0001623684760000041
Figure BDA0001623684760000051
in the above top-emitting OLED device with improved viewing angle characteristics, the light output coupling layer is a 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline material layer.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) the top-emitting OLED device with the improved visual angle characteristic firstly adopts the second electrode with the light transmittance not less than 25%, inhibits the effect of multi-beam interference in the microcavity effect, improves the visual angle characteristic, but after the multi-beam interference is inhibited, the wide-angle interference in the microcavity effect plays a role, and in order to inhibit the wide-angle interference, the top-emitting OLED device adopts an organic material with a high refractive index as a hole injection layer: the hole injection layer has a refractive index greater than or equal to 1.8. The high-refractive-index hole injection layer is matched with the ultrathin second electrode structure, so that the condition that the interference between the reflected light of the first electrode and the emitted light of the light-emitting layer is enhanced can be destroyed, the wide-angle interference in the OLED device is weakened, the microcavity effect is restrained, and the visual angle characteristic of the OLED device is improved. Meanwhile, the thickness of the hole injection layer is reduced due to the improvement of the refractive index of the hole injection layer, so that the overall thickness of the device is reduced, and materials and working hours can be saved in the production of the device.
(2) The top-emitting OLED device with the improved visual angle characteristic is additionally provided with the light output coupling layer, the light output coupling layer is made of 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline materials with low light absorption rate or ZnSe, ZnS and other high-refractive-index materials, and the light output coupling layer can reduce reflection of a semitransparent metal electrode, increase the output rate of internal light and further improve the visual angle characteristic of the device.
Drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the embodiments of the present disclosure taken in conjunction with the accompanying drawings, in which
FIG. 1 is a schematic view of a top-emitting OLED device with improved viewing angle characteristics according to embodiments 1-7 of the present invention;
FIG. 2 is a graph showing the refractive index of a tertiary amine compound selected in the present invention as a function of wavelength and the refractive index of 4,4' -tris [ phenyl (m-tolyl) amino ] triphenylamine as a function of wavelength.
The reference numbers in the figures denote: 1-substrate, 2-first electrode, 3-hole injection layer, 4-hole transport layer, 5-luminescent layer, 6-electron transport layer, 7-second electrode, 8-light output coupling layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
Example 1
The present embodiment provides a top-emitting OLED device with improved viewing angle characteristics, as shown in fig. 1, including a substrate 1, and a first electrode 2, a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, an electron transport layer 6, a second electrode 7, and a light outcoupling layer 8 stacked on the substrate 1. Wherein when the light-emitting wavelength of the light-emitting layer 5 is in the visible light band, the refractive index of the hole injection layer 3 is not less than 1.8. The thickness of the first layer is 10nm to 30nm, preferably 10 to 15 nm. The light output coupling layer 8 is made of 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline material with low light absorption rate or ZnSe, ZnS and other high-refractive-index materials, and the thickness of the material is 55 nm.
In this embodiment, the first electrode 2 is used as an anode and includes a first Ag layer for total reflection and a transparent ITO layer disposed on the first Ag layer, wherein the thickness of the first Ag layer is 150nm, and the thickness of the ITO layer is 20 nm.
The second electrode 7 is used as a cathode, and may be ITO, IZO or metallic silver, or may be a composite structure including a first metal layer and a second metal layer, wherein the first metal layer is an alkali metal or an alloy thereof, an alkaline earth metal or an alloy thereof, and the second metal layer is metallic silver; in this embodiment, the second electrode preferably includes a first metal layer and a second metal layer, wherein the first metal layer is Mg: the second metal layer of the Ag layer is metal silver, wherein Mg: the thickness of the Ag material layer is 2nm, and the proportion relation of Mg and Ag is 4: 1, the thickness of the metallic silver is 14 nm.
A microcavity effect is formed between the first electrode 2 and the second electrode 7.
The light-emitting layer 5 is excited to emit light, and the emitted light is emitted in the direction of the first electrode 2 and the second electrode 7. The emitted light is reflected by the first electrode 2, passes through the hole injection layer 3, the hole transport layer 4, the light emitting layer 5, and the electron transport layer 6, and reaches the second electrode 7.
In this embodiment, the light emitting wavelength of the light emitting layer 5 is in a blue light band, that is, the light emitting wavelength is 460nm, the refractive index N of the hole injection layer is greater than or equal to 2.0, in this embodiment, the refractive index of the hole injection layer is selected to be 2.04, the thickness is selected to be 100nm to 105nm, the thickness can be selected according to actual needs, and the thickness of the hole injection layer 3 in this embodiment is preferably 103 nm. The thicknesses of the other layers in this example are: the thickness of the hole transport layer is 20nm, the thickness of the luminescent layer is 20nm, and the thickness of the electron transport layer is 35 nm.
The hole injection layer 3 and the hole transport layer 4 are made of a tertiary amine compound, and the structural formula of the hole injection layer in this embodiment is:
Figure BDA0001623684760000071
the material of the hole transport layer may be the same as the material of the hole injection layer, or may be a tertiary amine compound of another structural formula, and the structural formula of the material of the hole transport layer in this embodiment is:
Figure BDA0001623684760000072
In this embodiment, the light transmittance of the ultra-thin second electrode 7 is greater than or equal to 25%, which suppresses the effect of multi-beam interference in the microcavity effect, increases the light guiding rate and the transmittance, and simultaneously increases the refractive index of the hole injection layer 3, destroys the condition that the interference between the reflected light of the first electrode 2 and the emitted light of the light-emitting layer 5 is enhanced, and suppresses wide-angle interference, thereby weakening the microcavity effect and effectively improving the viewing angle characteristic of the top-emitting OLED device; in addition, the light output coupling layer can reduce the reflection of the semitransparent metal electrode, increase the output rate of internal light and further improve the optical property of the display device.
In addition, when the light emitted from the light emitting layer is in the visible light band, the material of the light emitting layer is selected according to the light emitting band. In the application, when the light-emitting waveband of the light-emitting layer is in a blue light waveband, a green light waveband and a red light waveband, the material selected by the light-emitting layer is the prior art. And this is not a point of the invention of the present application, and therefore, detailed description thereof will be omitted in the respective embodiments of the present application.
Example 2
On the basis of embodiment 1, the structure of the top-emitting OLED device in this embodiment is shown in fig. 1. The light emitting wavelength of the light emitting layer 5 in this embodiment is in a green light band, that is, the light emitting wavelength is 510nm, the refractive index N of the hole injection layer is greater than or equal to 1.9, in this embodiment, the refractive index of the hole injection layer is selected to be 1.93, the thickness is 150nm to 155nm, the thickness can be selected according to actual needs, and the thickness of the hole injection layer in this embodiment is preferably 153 nm. In this example, compared with example 1, the light emitting wavelength of the light emitting layer 5 is not uniform, and therefore, the material used for the light emitting layer is different. The thickness of the hole injection layer was varied in this example, and the thickness of each layer was the same as that of example 1.
In this embodiment, the structural formula of the material of the hole injection layer is:
Figure BDA0001623684760000081
the structural formula of the material of the hole transport layer is as follows:
Figure BDA0001623684760000091
in this embodiment, the light transmittance of the ultra-thin second electrode 7 is greater than or equal to 25%, which inhibits the effect of multi-beam interference in the microcavity effect, so that the light guiding rate and the light transmittance are improved, and at the same time, the refractive index of the hole injection layer 3 is also improved, thereby destroying the condition that the interference between the reflected light of the first electrode 2 and the emitted light of the light emitting layer 5 is enhanced, so as to effectively improve the viewing angle characteristic of the top-emitting OLED device.
Example 3
Unlike embodiments 1 and 2, the structure of the top-emitting OLED device in this embodiment is shown in fig. 1, the light-emitting wavelength of the light-emitting layer in this embodiment is in the red wavelength band, i.e. the light-emitting wavelength is 620nm, the refractive index N of the hole injection layer is greater than or equal to 1.8, the refractive index of the hole injection layer is selected to be 1.81, and the thickness is 200-; the thickness can be selected according to actual needs, and the thickness of the hole injection layer in the embodiment is preferably 203 nm. In this example, compared with example 1 or example 2, the light-emitting layer 5 has a different light-emitting wavelength, and therefore the material used for the light-emitting layer is different.
In this embodiment, the structural formula of the material of the hole injection layer is:
Figure BDA0001623684760000092
the structural formula of the material of the hole transport layer is as follows:
Figure BDA0001623684760000101
in this example, only the thickness of the hole injection layer was changed, and the thicknesses of the other layers were the same as those of example 1.
In this embodiment, the light transmittance of the second electrode 7 is greater than or equal to 25%, which inhibits the effect of multi-beam interference in the microcavity effect, so that the light guiding rate and the transmittance are improved, and meanwhile, the refractive index of the hole injection layer 3 is improved, so as to destroy the condition that the interference between the reflected light of the first electrode and the emitted light of the light emitting layer is enhanced, thereby effectively improving the viewing angle characteristic of the top-emitting OLED device.
Example 4
In this embodiment, the light emitting wavelength of the light emitting layer 5 is in a blue light band, that is, the light emitting wavelength is 460nm, the refractive index N of the hole injection layer is greater than or equal to 2.0, and the thickness is 100 nm. The thicknesses of the other layers in this example are: the thickness of the hole transport layer is 20nm, the thickness of the luminescent layer is 20nm, and the thickness of the electron transport layer is 35 nm.
The hole injection layer 3 and the hole transport layer 4 are made of tertiary amine compounds, and the structural formulas of the compounds are as follows:
Figure BDA0001623684760000102
Example 5
In this embodiment, the light emitting wavelength of the light emitting layer 5 is in a green light band, the refractive index N of the hole injection layer is greater than or equal to 1.90, and the thickness is 150 nm. The thickness of the hole transport layer is 20nm, the thickness of the luminescent layer is 20nm, and the thickness of the electron transport layer is 35 nm.
The hole injection layer 3 and the hole transport layer 4 are made of tertiary amine compounds, and the structural formula of the hole injection layer and the hole transport layer is as follows:
Figure BDA0001623684760000111
example 6
In this embodiment, the light emitting wavelength of the light emitting layer 5 is in a red light band, the refractive index N of the hole injection layer is not less than 1.8, and the thickness is 200 nm. The thickness of the hole transport layer is 20nm, the thickness of the luminescent layer is 20nm, and the thickness of the electron transport layer is 35 nm.
The hole injection layer 3 and the hole transport layer 4 are made of tertiary amine compounds, and the structural formulas of the compounds are as follows:
Figure BDA0001623684760000112
example 7
In this embodiment, the light emitting wavelength of the light emitting layer 5 is in a red light band, the refractive index N of the hole injection layer is not less than 1.8, and the thickness is 200 nm. The thickness of the hole transport layer is 20nm, the thickness of the luminescent layer is 20nm, and the thickness of the electron transport layer is 35 nm.
The hole injection layer 3 and the hole transport layer 4 are made of tertiary amine compounds, and the structural formulas of the compounds are as follows:
Figure BDA0001623684760000121
To further illustrate the advantages of the top-emitting OLED devices with improved viewing angle characteristics provided by the present invention, comparative examples 1-3 were designed and implemented to compare with the test results of examples 1-3 in the application.
Comparative example 1
This comparative example provides a top-emitting OLED device having the same specific structure as example 1, the only difference being that the hole injection layer material is m-MTDATA hole injection material, which is named in chinese: 4,4' -tris [ phenyl (m-tolyl) amino ] triphenylamine, having the molecular formula:
Figure BDA0001623684760000122
the refractive index of the material is 1.8 at the wavelength of 460 nm.
Comparative example 2
This comparative example provides a top-emitting OLED device, which has the same specific structure as example 2, the only difference being that the hole injection layer material is m-MTDATA hole injection material, which is named in chinese: 4,4' -tris [ phenyl (m-tolyl) amino ] triphenylamine, having the molecular formula:
Figure BDA0001623684760000131
the wavelength of the material is 1.73 when the wavelength is 510 nm.
Comparative example 3
This comparative example provides a top-emitting OLED device, the specific structure of which is the same as example 3, the only difference being that the hole injection layer material therein is m-MTDATA hole injection material, which is named in chinese: 4,4' -tris [ phenyl (m-tolyl) amino ] triphenylamine, having the molecular formula:
Figure BDA0001623684760000132
The refractive index of the material is 1.67 at the wavelength of 620 nm.
The structures of comparative examples 1 to 3 and examples 1 to 3 were tested for the shift amount of the emission peak in the case where the emission wavelength of the light emitting layer was the same and the viewing angles were all 60 degrees, and the results are shown in tables 1 to 3:
TABLE 1
Wavelength (460nm) Refractive index of hole injection layer Luminescence peak shift amount (Δ u 'v')
Example 1 2.04 0.021
Comparative example 1 1.8 0.035
TABLE 2
Wavelength (510nm) Refractive index of hole injection layer Luminescence peak shift amount (Δ u 'v')
Example 2 1.93 0.011
Comparative example 2 1.73 0.026
TABLE 3
Wavelength (620nm) Refractive index of hole injection layer Luminescence peak shift amount (. DELTA.u 'v')
Example 3 1.81 0.045
Comparative example 3 1.67 0.068
As can be seen from the data in tables 1 to 3, when the wavelengths at which the light emitting layers emit light are the same, the amount of emission peak shift can be effectively reduced in the case of the same viewing angle.
In addition, FIG. 2 shows the refractive index profile with respect to wavelength of the tertiary amine compound selected in the present invention and the refractive index profile with respect to wavelength of 4,4' -tris [ phenyl (m-tolyl) amino ] triphenylamine. It can be seen from the figure that the refractive index of the tertiary amine compounds selected in the present application is always greater than that of 4,4' -tris [ phenyl (m-tolyl) amino ] triphenylamine in the visible band (wavelength from 300nm to 600 nm). Therefore, the hole injection layer made of the material selected by the invention can effectively improve the refractive index of the hole injection layer, and can effectively destroy the condition of enhancing the interference between the reflected light of the first electrode 2 and the emitted light of the light-emitting layer 5, thereby effectively improving the viewing angle characteristic of the top-emitting OLED device.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.

Claims (6)

1. A top-emitting OLED device with improved visual angle characteristics is characterized by comprising a substrate, and a first electrode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, a second electrode and a light output coupling layer which are arranged on the substrate in a superposed mode; the light transmittance of the second electrode is not less than 25%, and the refractive index of the hole injection layer is not less than 1.8;
when the light-emitting wavelength of the light-emitting layer is in a green light band, the refractive index N of the hole injection layer is more than or equal to 1.9; when the light-emitting wavelength of the light-emitting layer is in a blue light band, the refractive index N of the hole injection layer is more than or equal to 2.0; when the light-emitting wavelength of the light-emitting layer is in a red light wave band, the refractive index N of the hole injection layer is more than or equal to 1.8;
the hole injection layer is used for destroying the condition that the interference between the reflected light of the first electrode and the emitted light of the light-emitting layer is enhanced, and reducing the light-emitting peak offset when the visual angle is 60 degrees;
The light output coupling layer is used for suppressing multiple beam interference in the microcavity effect formed by the first electrode and the second electrode.
2. The top-emitting OLED device with improved viewing angle characteristics of claim 1, wherein the second electrode is indium tin oxide or indium zinc oxide or metallic silver.
3. The top-emitting OLED device with improved viewing angle characteristics of claim 1, wherein the second electrode comprises a first metal layer and a second metal layer, wherein the first metal layer is an alkali metal or an alloy thereof, an alkaline earth metal or an alloy thereof, and the second metal layer is metallic silver.
4. The top-emitting OLED device with improved viewing angle characteristics of claim 3, wherein the thickness of the second electrode is 10nm-30 nm.
5. The top-emitting OLED device with improved viewing angle characteristics of any of claims 1 to 4, wherein the material of the hole injection layer has the formula:
Figure FDF0000016313090000011
Figure FDF0000016313090000021
Figure FDF0000016313090000031
6. the top-emitting OLED device with improved viewing angle characteristics of claim 1, wherein the light outcoupling layer is a 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline material layer.
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