CN106611769B - Organic electroluminescent element - Google Patents
Organic electroluminescent element Download PDFInfo
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- CN106611769B CN106611769B CN201510676867.3A CN201510676867A CN106611769B CN 106611769 B CN106611769 B CN 106611769B CN 201510676867 A CN201510676867 A CN 201510676867A CN 106611769 B CN106611769 B CN 106611769B
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- 239000011241 protective layer Substances 0.000 claims abstract description 70
- 239000010409 thin film Substances 0.000 claims abstract description 50
- 229910052709 silver Inorganic materials 0.000 claims abstract description 48
- 239000004332 silver Substances 0.000 claims abstract description 48
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000758 substrate Substances 0.000 claims abstract description 24
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Images
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/12—Active-matrix OLED [AMOLED] displays
- H10K59/122—Pixel-defining structures or layers, e.g. banks
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/12—Active-matrix OLED [AMOLED] displays
- H10K59/1201—Manufacture or treatment
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The present invention provides an organic electroluminescent element comprising: a thin film transistor array substrate; an organic light emitting diode comprising: an anode comprising a silver film, the anode disposed on the thin film transistor array and electrically connected to the thin film transistor; an organic functional layer, which at least comprises an organic light-emitting layer and is positioned on the anode; a cathode, said cathode being located over the organic functional layer; and a pixel definition layer for defining a pixel region; a protective layer between the anode and the pixel defining layer; and the packaging cover plate is positioned on the light-emitting side of the organic light-emitting diode so as to package the organic light-emitting diode in a sealing space between the packaging cover plate and the thin film transistor array substrate. The protective layer can prevent silver ions from migrating and prevent the silver film from deteriorating.
Description
Technical Field
The present invention relates to an organic electroluminescent element (OLED), and more particularly, to an organic electroluminescent element that prevents silver ion migration and deterioration of a silver thin film.
Background
In the OLED display technology, an active organic electroluminescent device (AMOLED) displays an image by controlling light emission of an organic light emitting material using a current. In such devices, a Thin Film Transistor (TFT) array substrate including scan lines, signal lines and TFTs is required to implement the driving and controlling functions of the organic light emitting diode by current, and the current passes through a resonant cavity between an anode and a cathode to perform electron and hole resonance, thereby generating the excitation of the OLED material to generate light emission.
In the top-emission type OLED device, a reflective anode electrode is used as the anode, and light emitted from the light-emitting layer is reflected by the reflective anode electrode and emitted from the upper surface. As shown in fig. 1, an anode 1 is located on a planarization layer (not shown) and is in contact with a pixel defining layer 2, and the anode 1 is generally formed by laminating a first ITO layer (indium tin oxide) 11 as an anode contact layer, a metal layer 12 as a reflective layer, and a second ITO layer 13. The first ITO layer 11 and the second ITO layer 13 have the advantages of good conductivity, high transmittance, high work function, and the like, and can effectively improve the display efficiency. The reflective layer is required to have high reflectance and low resistivity, and a metallic silver thin film 12 having high reflectance and low absorption in the visible light region and good conductivity is generally used. The pixel defining layer 2 covers the side surface and a part of the upper surface of the anode 1, and is in contact with the silver thin film 12 at the side surface of the anode 1.
The inventors of the present invention found that, when SEM analysis was performed on the interface between the anode 1 and the pixel defining layer 2 in the prior art, the silver thin film 12 in the anode 1 was raised, as shown in fig. 2. The current of the device is easily concentrated at the raised part in the subsequent discharging process, so that the silver ion migration is easily generated on the defective silver film 12, the short circuit is easily generated between the cathode and the anode, and further, a sub-pixel dark spot is generated during the light emitting process, and the light emitting effect is influenced.
Disclosure of Invention
In view of the disadvantages in the prior art, the present invention provides an organic electroluminescent device, comprising:
a thin film transistor array substrate;
an organic light emitting diode comprising:
an anode comprising a silver film, the anode disposed on the thin film transistor array and electrically connected to the thin film transistor;
an organic functional layer, which at least comprises an organic light-emitting layer and is positioned on the anode;
a cathode, said cathode being located over the organic functional layer; and
a pixel defining layer for defining a pixel region;
a protective layer between the anode and the pixel defining layer; and
and the packaging cover plate is positioned on the light-emitting side of the organic light-emitting diode so as to package the organic light-emitting diode in a sealing space between the packaging cover plate and the thin film transistor array substrate.
Further, the protective layer covers at least the anode portion in contact with the pixel defining layer.
Further, the protective layer covers only the anode portion in contact with the pixel defining layer.
Further, the protective layer is made of an inorganic material.
Further, the protective layer material is nitride or oxynitride.
Further, the thickness of the protective layer is larger than
Further, the protective layer covers at least a side surface and an upper surface of the anode.
Further, the protective layer is made of a conductive semiconductor material.
Further, the protective layer material is indium tin oxide.
Further, the thickness of the protective layer is
Further, the anode further comprises a first conductive layer and a second conductive layer, and the silver film is positioned between the first conductive layer and the second conductive layer.
Compared with the prior art, the invention has at least the following effects:
1. the protective layer can effectively prevent the silver film in the anode from rising, so that the phenomenon that the cathode and the anode are short-circuited to influence the luminous effect due to the migration of silver ions in the discharging process is prevented.
2. The organic material used by the pixel defining layer contains sulfide and oxide, and the metal silver is active and unstable in property and is easy to be vulcanized and oxidized.
Drawings
FIG. 1 is a schematic diagram of a structure of an anode and a pixel defining layer in the prior art;
FIG. 2 is an SEM image of the interface of a silver thin film and a pixel defining layer;
FIG. 3 is a schematic diagram showing the analysis of the interfacial force between the silver thin film and the pixel defining layer in the anode;
FIGS. 4A to 4F are schematic views illustrating a process of preparing a protective layer of an anode according to an embodiment of the present invention;
fig. 5A to 5E are schematic views illustrating a process of preparing a protective layer of an anode according to another embodiment of the present invention.
Wherein the reference numerals are as follows:
1: anode 11: first ITO layer
12: silver thin film 13: second ITO layer
2: pixel definition layer 3: protective layer
4: photoresist mask
Detailed Description
Example embodiments will now be described more fully with reference to the accompanying drawings. Example embodiments may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of example embodiments to those skilled in the art. The same reference numerals in the drawings denote the same or similar structures, and thus their repetitive description will be omitted.
The description of the directions and positions of the upper, lower, middle, upper and the like in the present invention is provided by the accompanying drawings as an example, but may be changed as required, and all the changes are included in the scope of the present invention. The terms first and second are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated.
The present inventors have investigated the cause of the problem in relation to the phenomenon of the silver thin film 12 bulging in the anode 1. In the prior art, an ITO/Ag/ITO combination is adopted for the anode 1, and the stress values of an ITO layer and a silver film in the combination are detected. The test instrument is a membrane stress tester generally known or used on the market. The detection method comprises the following steps: placing the silicon wafer attached to the substrate into a film stress tester, and detecting the film stress of the silicon wafer before film coating to obtain a previous value A; taking out the silicon wafer, and plating a film to be detected for the stress value on the silicon wafer; and (3) placing the silicon wafer plated with the film into a film stress tester for detection to obtain a back value B, and subtracting the front value A from the back value B to obtain the stress value of the film.
The detection is carried out by adopting the method, and in the reflecting anode electrode, the stress value of the silver thin film 12 is-34 mPa, and the stress type is compressive stress (compression). The first ITO layer 11 and the second ITO layer 13 have a stress value of-167 mPa and a stress type of compressive stress (compression). And the pixel defining layer 2 has a stress value of 3400mPa and the stress type is Tensile stress (Tensile). Therefore, as shown in fig. 3 (a) and (b), a tensile film stress is generated when the silver film 12 is in contact with the pixel defining layer 2. As shown in fig. 3, when both stresses are Isotropic stresses (Isotropic Stress), a Mud crack (Mud Flat Cracks) phenomenon shown in fig. 3 (c) occurs on the contact surface of the silver thin film 12 and the pixel defining layer 2; when both the stresses are Anisotropic stresses (Anisotropic stresses), Straight Cracks (Straight Cracks) as shown in fig. 3 (d) are generated on the contact surface of the silver thin film 12 and the pixel defining layer 2.
Through the above analysis, when the silver thin film 12 is in contact with the pixel defining layer 2 after the anode 1 process is completed, the silver thin film 12 may be pulled by the tensile stress of the pixel defining layer 2 to cause the above-mentioned doming phenomenon due to the difference in film stress and stress type between the silver thin film 12 and the pixel defining layer 2.
In addition, the pixel defining layer 2 can be formed by some photosensitive materials, polymer materials, silicon oxides, and silicon nitrides, the used materials contain a small amount of sulfides and/or oxides, and the metal silver is active and unstable, and the silver film 12 is thin, and the silver film 12 can be damaged by the small amount of sulfides and oxides, so that the silver film 12 can be easily vulcanized and oxidized.
In order to avoid the above phenomenon, the present invention provides an organic electroluminescent device comprising: the light emitting diode package comprises a Thin Film Transistor (TFT) array substrate, an Organic Light Emitting Diode (OLED) positioned on the TFT array substrate, a protective layer and a package cover plate.
The TFT array of the present invention includes: the structure of the active layer, the gate electrode, the gate insulating layer, the source electrode, the drain electrode, the passivation layer, the planarization layer and the like can be formed in sequence according to the film structure process technology (deposition, photoetching and other processes) in the prior art.
The organic light emitting diode is disposed above the TFT array and electrically connected to the thin film transistor, and includes: an anode 1, an organic functional layer (not shown) formed over the anode 1, a cathode (not shown) positioned over the organic functional layer, and a pixel defining layer 2. Fig. 4F and 5E show only the anode 1 and pixel defining layer 2 structures.
The anode 1 in the present invention includes a silver thin film 12 serving as a reflective layer. The silver thin film 12 may be a pure silver thin film or a silver alloy thin film containing at least one element selected from Pd, Cu, Ti, Nb, Al, Pb, Au, Nd, Ca, and Mg. The anode 1 may further include a first conductive layer and a second conductive layer with the silver thin film 12 therebetween.
The anode 1 may be formed by laminating the silver thin film 12 with a first conductive layer and a second conductive layer made of other conductive semiconductor materials, which may be any conductive glass that may be used as an anode of an organic light emitting diode, including, but not limited to, Indium Tin Oxide (ITO), aluminum-doped zinc oxide (AZO), indium-doped zinc oxide (IZO), antimony-doped tin dioxide (ATO), or fluorine-doped tin oxide (FTO). In one embodiment, the first conductive layer and the second conductive layer are ITO layers, and the anode 1 is formed by sequentially laminating a first ITO layer 11, a silver thin film 12, and a second ITO layer 13, and the anode laminated structure is described as an example in the drawings and the embodiments. The anode 1 may be formed using process techniques known in the art.
The organic functional layer at least comprises an organic light-emitting layer, and can further comprise one or more layers of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer and an electron injection layer. The organic functional layer can be formed sequentially by using materials and process technology in the prior art.
For the cathode, an alkali metal, an alkaline earth metal, a transition metal, a group 13 metal of the periodic table, an alloy of the above metals, or the like can be used, and a transparent conductive electrode made of a conductive metal oxide, a conductive organic substance, a conductive semiconductor material, or the like can also be used. Examples include: metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, magnesium-silver alloys, magnesium-indium alloys, magnesium-aluminum alloys, indium-silver alloys, lithium-aluminum alloys, lithium-magnesium alloys, lithium-indium alloys, calcium-aluminum alloys, and the like, conductive metal oxides such as indium oxide, zinc oxide, tin oxide, Indium Tin Oxide (ITO), and indium-doped zinc oxide (IZO), and conductive semiconductor materials. The cathode may be formed using prior art process techniques.
Referring to fig. 4F and 5E, a pixel defining layer 2 of the organic light emitting diode covers a side surface and a portion of a first surface (an upper surface in the illustration of the embodiment) of an anode 1 to define a pixel region, and a protective layer 3 is disposed between the anode 1 and the pixel defining layer 2, wherein the protective layer 3 separates the anode 1 from the pixel defining layer 2 to protect the anode 1.
The protective layer 3 can effectively prevent the silver film 12 in the anode 1 from swelling, thereby preventing silver ions from migrating in the discharging process, avoiding the phenomenon of short circuit between the cathode and the anode, and improving the luminous effect. Since the anode 1 and the pixel defining layer 2 are separated by the protective layer 3, the protective layer 3 can function to prevent the silver thin film 12 in the anode 1 from being vulcanized or oxidized.
The protective layer 3 may cover a part of the anode 1, as shown in fig. 4F, wherein the protective layer 3 covers at least a part of the anode in contact with the pixel defining layer 2, including the side surfaces and a part of the upper surface of the anode 1. In some embodiments, the protective layer 3 may further extend from the side of the anode 1 to the non-light emitting region, for example, to a region between the pixel defining layer 2 and the planarizing layer. The protective layer 3 preferably covers only the anode portion in contact with the pixel defining layer 2, whereby the protective layer 3 does not block upward emission of light reflected by the silver thin film 12, thereby contributing to an increase in aperture ratio. When the protective layer 3 covers part of the anode 1, the protective layer 3 may be made of an inorganic material, and the stress value and the stress type of the protective layer 3 made of the inorganic material are similar to those of the anode 1. The thickness of the protective layer 3 formed of an inorganic material may be greater than
Useful inorganic materials include, but are not limited to, one of the following and combinations thereof: the oxide, nitride, oxynitride, and fluoride are preferable, and the oxide, nitride, and oxynitride are more preferable. Oxides include, but are not limited to, alumina, zirconia, zinc oxide, titania, magnesia, silica. Nitrides include, but are not limited to, silicon nitride, aluminum nitride, titanium nitride. Oxynitrides include, but are not limited to, silicon oxynitride, aluminum oxynitride, titanium oxynitride. Fluorides include, but are not limited to, magnesium fluoride, sodium fluoride.
Methods for preparing the protective layer 3 from inorganic materials include, but are not limited to, evaporation, sputtering, spin coating, spray coating, screen printing, ink jet printing, Chemical Vapor Deposition (CVD).
The protective layer 3 may also be a transparent protective layer covering the side surfaces and the entire upper surface of the anode 1, and as shown in fig. 5E, the protective layer 3 covers the portion of the anode in contact with the pixel defining layer 2, including the anode side surfaces and the entire upper surface. In some embodiments, the protective layer 3 may further extend from the side of the anode 1 to the non-light emitting region, for example, to a region between the pixel defining layer 2 and the planarizing layer. When the protective layer 3 covers the side surfaces and the entire upper surface of the anode 1, the protective layer 3 may be made of a conductive semiconductor material, preferably a semiconductor material having high transparency, so as to increase the transmittance of light reflected by the silver thin film 12. The thickness of the protective layer 3 may be formed
Preference is given to
Useful conductive semiconductor materials include, but are not limited to, one of Indium Tin Oxide (ITO), aluminum-doped zinc oxide (AZO), indium-doped zinc oxide (IZO), antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), or combinations thereof, preferably Indium Tin Oxide (ITO).
Methods of preparing the protective layer 3 from the transparent conductive semiconductor material include, but are not limited to, evaporation, sputtering, spin coating, spray coating, screen printing, ink jet printing, Chemical Vapor Deposition (CVD).
The embodiment of the invention also provides a preparation method of the organic electroluminescent element, which comprises the following steps:
the method comprises the following steps: providing a substrate which can be a rigid substrate or a flexible substrate, including but not limited to a glass substrate, a quartz substrate, a metal substrate, an organic polymer substrate, a metal oxide substrate, and cleaning the substrate by using a prior art method including ultrasonic cleaning;
step two: manufacturing a TFT array on the cleaned glass substrate, wherein the related process flow comprises the following steps of 1: preparing a polysilicon layer, and step 2: preparing a grid, and step 3: preparing an insulating layer, and step 4: forming a data line layer, and a step 5: preparing a buffer layer, and 6: preparing a planarization layer;
step three: the organic light emitting diode is prepared on the TFT array, and the related process flow comprises the following steps of 1: preparing an anode 1, and a step 2: preparing a protective layer 3, and step 3: preparing a pixel definition layer 2, and a 4 th step: preparing an organic functional layer, wherein the organic functional layer at least comprises an organic light-emitting layer, and the step 5: and preparing a cathode.
Step four: and providing a packaging cover plate, wherein the material of the cover plate can be the same as or different from that of the substrate, performing a packaging process, and packaging the organic light-emitting diode in a sealed space between the packaging cover plate and the thin film transistor array substrate to form the organic electroluminescent element.
The process for producing the protective layer 3 of the present invention is described in detail below by way of examples.
Example 1:
referring to fig. 4A to 4F, after the anode 1 is completed, a protective layer 3 composed of an inorganic material is prepared on the anode 1, and the protective layer 3 in the present embodiment covers the side surfaces and a part of the upper surface of the anode 1.
The preparation process comprises the following steps:
step S1: as shown in fig. 4A and 4B, after the anode 1 is completed, a protective layer 3 composed of an inorganic material is prepared on the side and upper surfaces of the anode 1;
step S2: as shown in fig. 4C, a photoresist mask 4 is formed on the protective layer 3;
step S3: as shown in fig. 4D, the protective layer 3 not covered with the photoresist mask 4 is removed by etching;
step S4: as shown in fig. 4E, the resist mask 4 is stripped off to form the protective layer 3.
Step S5: next, the pixel defining layer 2 is formed on the protective layer 3, as shown in fig. 4F.
Example 2:
referring to fig. 5A to 5E, after the anode 1 is completed, a protective layer 3 composed of a conductive semiconductor material is prepared on the anode 1, and the protective layer 3 in the present embodiment covers the side surfaces and the entire upper surface of the anode 1.
The preparation process comprises the following steps:
step S1': as shown in fig. 5A and 5B, after the anode 1 is completed, a protective layer 3 composed of a conductive semiconductor material is prepared on the side and upper surfaces of the anode 1;
step S2': as shown in fig. 5C, a photoresist mask 4 is formed on the protective layer 3 to cover a predetermined region of the protective layer 3;
step S3': as shown in fig. 5D, the excess protective layer structure is etched, and the photoresist mask 4 is stripped to form the protective layer 3.
Step S4': next, a pixel defining layer 2 is prepared on the protective layer 3, as shown in fig. 5E.
Exemplary embodiments of the present invention are specifically illustrated and described above. However, those skilled in the art will appreciate that various modifications and substitutions can be made to the specific embodiments of the present invention without departing from the spirit and scope of the invention. Such modifications and substitutions are intended to be included within the scope of the present invention as defined by the appended claims.
Claims (3)
1. An organic electroluminescent element, comprising:
a thin film transistor array substrate;
an organic light emitting diode comprising:
an anode comprising a silver thin film, a first conductive layer and a second conductive layer, the anode disposed on the thin film transistor array and electrically connected to the thin film transistor; the silver film is positioned between the first conductive layer and the second conductive layer;
an organic functional layer, which at least comprises an organic light-emitting layer and is positioned on the anode;
a cathode, said cathode being located over the organic functional layer; and
a protective layer and a pixel defining layer for defining a pixel region, wherein the protective layer is directly formed on the anode and the pixel defining layer is directly formed on the protective layer; the protective layer separates the side of the silver thin film from the pixel defining layer to prevent the side of the silver thin film from contacting the pixel defining layer; the protective layer at least covers the anode part which is in contact with the pixel defining layer, the protective layer is made of inorganic materials, and the materials of the protective layer are nitrides or oxynitrides; and
and the packaging cover plate is positioned on the light-emitting side of the organic light-emitting diode so as to package the organic light-emitting diode in a sealing space between the packaging cover plate and the thin film transistor array substrate.
2. The organic electroluminescent element according to claim 1, wherein the protective layer has a thickness greater than that of the organic electroluminescent element
3. An organic electroluminescent element, comprising:
a thin film transistor array substrate;
an organic light emitting diode comprising:
an anode comprising a silver thin film, a first conductive layer and a second conductive layer, the anode disposed on the thin film transistor array and electrically connected to the thin film transistor; the silver film is positioned between the first conductive layer and the second conductive layer;
an organic functional layer, which at least comprises an organic light-emitting layer and is positioned on the anode;
a cathode, said cathode being located over the organic functional layer; and
a protective layer and a pixel defining layer for defining a pixel region, wherein the protective layer is directly formed on the anode and the pixel defining layer is directly formed on the protective layer; the protective layer separates the side of the silver thin film from the pixel defining layer to prevent the side of the silver thin film from contacting the pixel defining layer; the protective layer covers only the anode portion in contact with the pixel defining layer; and
and the packaging cover plate is positioned on the light-emitting side of the organic light-emitting diode so as to package the organic light-emitting diode in a sealing space between the packaging cover plate and the thin film transistor array substrate.
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| CN110518053A (en) * | 2019-08-29 | 2019-11-29 | 合肥鑫晟光电科技有限公司 | Display base plate and preparation method thereof, display device |
| CN111987243B (en) * | 2020-08-11 | 2021-11-02 | Tcl华星光电技术有限公司 | Display panel manufacturing method and display panel |
| CN114203890B (en) * | 2021-12-10 | 2024-01-26 | Tcl华星光电技术有限公司 | Display panel and preparation method of display panel |
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| CN116782708B (en) * | 2023-06-20 | 2024-03-26 | 深圳市鸿展光电有限公司 | AMOLED display device with high brightness and high contrast and manufacturing process thereof |
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