WO2014134839A1 - 一种二极管及其制作方法、显示装置 - Google Patents

一种二极管及其制作方法、显示装置 Download PDF

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WO2014134839A1
WO2014134839A1 PCT/CN2013/072488 CN2013072488W WO2014134839A1 WO 2014134839 A1 WO2014134839 A1 WO 2014134839A1 CN 2013072488 W CN2013072488 W CN 2013072488W WO 2014134839 A1 WO2014134839 A1 WO 2014134839A1
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layer
diode
transparent metal
metal layer
transparent
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French (fr)
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李金川
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TCL China Star Optoelectronics Technology Co Ltd
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Shenzhen China Star Optoelectronics Technology Co Ltd
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Publication of WO2014134839A1 publication Critical patent/WO2014134839A1/zh
Priority to US14/530,825 priority patent/US9799855B2/en
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    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/805—Electrodes
    • H10K59/8051—Anodes
    • H10K59/80517—Multilayers, e.g. transparent multilayers
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
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    • H10K50/81—Anodes
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/82—Cathodes
    • H10K50/824—Cathodes combined with auxiliary electrodes
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/82—Cathodes
    • H10K50/828—Transparent cathodes, e.g. comprising thin metal layers
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    • 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
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/805—Electrodes
    • H10K59/8052—Cathodes
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    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/805—Electrodes
    • H10K59/8052—Cathodes
    • H10K59/80524—Transparent cathodes, e.g. comprising thin metal layers
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    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/302—Details of OLEDs of OLED structures
    • H10K2102/3023—Direction of light emission
    • H10K2102/3031—Two-side emission, e.g. transparent OLEDs [TOLED]
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Definitions

  • the invention relates to a diode, a manufacturing method thereof and a display device.
  • Conventional double-sided light-emitting organic light-emitting diodes are generally prepared by sequentially preparing a single-layer transparent anode and an organic layer (including a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer) on a glass substrate.
  • Metal cathode and passivation layer are generally prepared by sequentially preparing a single-layer transparent anode and an organic layer (including a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer).
  • the double-sided light-emitting diode In order to obtain a good transmittance, the double-sided light-emitting diode usually has a very thin cathode, which is generally easy to cause excessive cathode resistance and poor contact between the cathode and the peripheral circuit of the diode, so that the performance and reliability of the diode are compared. Poor, the service life is not long, and the transmittance of this diode is only about 50%.
  • the technical problem to be solved by the present invention is to provide a diode, a manufacturing method thereof and a display device, which can greatly improve the transmittance and luminous efficiency of the diode, enhance the reliability of the diode, and prolong the service life of the diode.
  • one technical solution adopted by the present invention is to provide a diode, the diode comprising: a composite anode, the composite anode comprising a transparent anode layer and a first transparent metal layer, the first transparent metal layer Formed on the transparent anode layer; a transparent metal oxide layer formed on the first transparent metal layer; a main structural layer, the main structural layer being formed on the transparent metal Above the oxide layer; a composite cathode comprising two second transparent metal layers, the two second transparent metal layers being formed on the body structure layer.
  • the composite cathode further includes an opaque metal layer formed on at least one edge of the second transparent metal layer, the area of the opaque metal layer being smaller than the area of the second transparent metal layer One-fifth.
  • the diode further comprises an anti-reflection film layer, and the anti-reflection film layer is formed on the opaque metal layer.
  • the diode further comprises a barrier layer, the barrier layer is formed on the anti-reflection film layer, and the barrier layer is a water-oxygen barrier film layer.
  • the main structure layer includes a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer which are sequentially formed on the transparent metal oxide layer.
  • the first transparent metal layer is a gold or silver metal layer having a thickness of 5-10 nm.
  • the transparent metal oxide layer has a thickness of 1-5 nm, and a difference between a work function of the metal oxide and a highest occupied orbital value of the electron injection layer material of the diode is 0 to 1 eV.
  • the difference between the work function of the metal oxide and the highest occupied orbital value of the electron injecting layer material of the diode is 0 eV.
  • the two second transparent metal layers are respectively a magnesium metal layer and a magnesium and silver metal layer having a thickness of 5-15 nm, and the opaque metal layer is an aluminum metal layer having a thickness of 50-250 nm.
  • the material of the antireflection film layer is a hole transport layer material or an electron transport layer material used as the diode.
  • the antireflection coating layer is a n-bromopropane layer having a thickness of 10 to 80 nm.
  • another technical solution provided by the present invention is to provide a display device including the above-described diode and a cover plate.
  • another technical solution adopted by the present invention is to provide a method for manufacturing a diode, comprising: depositing a transparent anode layer on a glass substrate, and depositing a vapor on the transparent anode.
  • a transparent metal layer, the transparent anode layer and the first transparent metal layer constitute a composite anode; a transparent metal oxide layer is evaporated on the first transparent metal layer; on the transparent metal oxide layer
  • the main body layer is vapor-deposited; and two second transparent metal layers are successively vapor-deposited on the main structural layer.
  • the method further includes: depositing an opaque metal layer on at least one edge of the second transparent metal layer, The area of the opaque metal layer is less than one fifth of the area of the second transparent metal layer.
  • the method further comprises: depositing an anti-reflection film layer on the opaque metal layer.
  • the method further comprises: covering the anti-reflection film layer with a barrier layer, the barrier layer being a water-oxygen barrier film Floor.
  • the barrier layer comprises a third transparent metal layer and two film layers, and the third transparent metal layer is formed between the two film layers.
  • the material of the antireflection film layer is a hole transport layer material or an electron transport layer material used as the diode.
  • the diode structure of the present invention uses a composite structure in which a composite anode, a transparent metal oxide layer and a composite cathode are combined, so that the structural layers of the diode can be matched in the energy level.
  • the luminous efficiency and brightness of the diode from the substrate surface are greatly improved, the luminous performance and reliability of the diode are enhanced, and the service life of the diode is prolonged.
  • FIG. 1 is a schematic structural view of an embodiment of a diode of the present invention.
  • FIG. 2 is a schematic structural view of another embodiment of a diode of the present invention.
  • FIG. 3 is a schematic structural view of an embodiment of a display device of the present invention.
  • Figure 4 is a schematic view showing the brightness comparison of the diode of the present invention.
  • Figure 5 is a schematic view showing the comparison of the pixel shrinkage effect of the diode of the present invention.
  • Figure 6 is a flow chart of one embodiment of a method of fabricating a diode of the present invention.
  • an embodiment of a diode of the present invention includes a composite anode 11, a transparent metal oxide layer 12, a bulk structure layer 13, and a composite cathode 14.
  • a composite anode 11 includes a composite anode 11, a transparent metal oxide layer 12, a bulk structure layer 13, and a composite cathode 14.
  • the composite anode 11 includes a transparent anode layer 21 and a first transparent metal layer 22 formed on the transparent anode layer 21, the first transparent metal layer 22 being a thin high-purity metal layer, thickness control It can achieve transparency and the penetration rate can reach more than 90%.
  • a gold or silver metal layer having a thickness of 5 to 10 nm and a purity of 99.999% or more may be deposited as a first transparent metal layer 22 over the conventional transparent anode layer 21.
  • a silver metal layer having a thickness of 10 nm is used as the first transparent metal layer 22.
  • a transparent metal oxide layer 12 is formed over the first transparent metal layer 22.
  • the thickness of the transparent metal oxide layer 12 is preferably controlled to be between 1 and 5 nm.
  • a material having a work function and a hole-injecting layer material of the diode having a highest occupied orbital (HOMO) value (the difference range of 0-1 eV) may be selected as the material of the metal oxide layer 12, and a work function is preferably selected.
  • a material having the same HOMO value as the hole injection layer material of the diode is used as the material of the metal oxide layer 12.
  • WO 3 can be selected as the material of the metal oxide layer.
  • the main structure layer 13 is formed on the transparent metal oxide layer 12, and the main structure layer 13 is a main component of a diode, and generally includes a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer.
  • the hole injection layer, the hole transport layer, the light-emitting layer, the electron transport layer, and the electron injection layer are sequentially formed on the transparent metal oxide layer 12, respectively.
  • the composite cathode 14 includes two second transparent metal layers, respectively a second transparent metal layer I23 and a second transparent metal layer II24.
  • the second transparent metal layer I23 and the second transparent metal layer II24 are sequentially formed on the main structure layer 13 respectively.
  • Upper that is, formed directly on the electron injection layer.
  • the composite cathode further includes an opaque metal layer 25 formed on at least one edge of the second transparent metal layer II24, the area being less than five-fifth of the area of the second transparent metal layer II24.
  • a second transparent metal layer I23 is evaporated on the entire light-emitting region, and a second transparent metal layer II24 is deposited on the second transparent metal layer I23, wherein the second transparent metal layer 23 and the second transparent metal Layer II24 may be a magnesium (Mg):silver (Ag) metal layer and a silver (Ag) metal layer having a thickness of 5-15 nm, respectively, to ensure good transmittance.
  • a relatively thick opaque metal layer 25 is further evaporated on any one or several sides of the second transparent metal layer II24.
  • the thickness of the opaque metal layer 25 is greater than 50 nm, such as a metal aluminum layer of 50-250 nm, and more preferably The thickness ranges from 60 to 90 nm, most preferably 80 nm.
  • the opaque metal layer 25 is partially opaque, and the other portions of the cathode are transparent, which can ensure the double-sided illuminating effect of the diode of the present invention.
  • the diode is better in energy level matching.
  • the efficiency and brightness of the diode are greatly improved compared with the traditional structure diode.
  • the diode of the present invention further includes an anti-reflection coating layer 26 formed on the opaque metal layer 25 as an out-coupling luminescent layer to further improve the luminescent properties of the diode.
  • the anti-reflection film layer 26 may be selected from a lower cost organic material, such as a material used as a diode hole transport layer or an electron transport layer, but the selected material is not suitable for absorption of visible light, and the material should be stable after film formation. There will be no crystallization phenomenon.
  • n-bromopropane (NPB) can be used as the material of the antireflection coating layer 26.
  • the thickness of the antireflection coating layer 26 is preferably controlled to be in the range of 10 to 80 nm, more preferably in the range of 50 to 70 nm, and most preferably in the range of 60 nm.
  • the display device is obtained by attaching a desiccant in a non-light-emitting area of the diode and then encapsulating it through an NV glue, which causes an increase in the area of the non-light-emitting area of the diode, so that the frame of the display device is wider and affects the appearance.
  • the diode of the present invention further comprises a barrier layer, which is a water-oxygen barrier film layer.
  • the barrier layer is used to replace the conventional desiccant layer and can be any film that blocks water oxygen.
  • a laminate of a plurality of film layers can be generally used as a barrier layer. More preferably, a sandwich layer of two film layers, that is, a film layer I27, a film layer II29, and a third transparent metal layer 28 is used.
  • the structure serves as a barrier layer (the structural layers labeled 27, 28, 29 in the illustrated structure collectively form a barrier layer).
  • the film material used as the barrier layer may be a less expensive organic or inorganic material such as lithium quinolate (Liq) .
  • the film layer I27 and the film layer II29 may be made of different materials or may be made of the same material.
  • the thickness of the film layer I27 and the film layer II29 is preferably controlled to be 10 to 60 nm, more preferably in the range of 20 to 50 nm, and most preferably 40 nm.
  • the material of the third transparent metal layer 28 may be a relatively inexpensive metal such as aluminum, copper or the like.
  • the thickness of the third transparent metal layer 28 is preferably controlled to be 1-10 nm, more preferably the thickness is in the range of 1-5 nm, and most preferably 2 nm.
  • the present invention further provides an embodiment of a display device.
  • FIG. 3 it is a schematic structural diagram of an embodiment of a display device according to the present invention, wherein:
  • the display device comprises a glass substrate 31, a diode 32 and a cover plate 33.
  • the diode 32 is formed on the glass substrate 31.
  • the diode 32 can be the diode mentioned in any of the above embodiments.
  • the diode 32 is covered by UV glue or FRIT glue 34.
  • the board 33 is packaged to form a display device.
  • the display device obtained by using the diode package in the embodiment of the invention has a narrow frame and a beautiful appearance.
  • the transparent anode layer 21 is ITO;
  • the first transparent metal layer 22 is Ag, having a purity of 99.999% and a thickness of 10 nm;
  • the transparent metal oxide layer 12 is WO 3 and has a HOMO of 5.7 eV, which is close to the HOMO 5.3 eV/5.4 eV of the hole injection layer or the transport layer;
  • the main structure layer 13 is a hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer (HIL/HTL/EML/ETL/EIL);
  • the second transparent metal layer I23 is Mg:Ag, and has a thickness of 10 nm;
  • the second transparent metal layer II24 is Ag and has a thickness of 10 nm;
  • the opaque metal layer 25 is Al and has a thickness of 80 nm;
  • the anti-reflection coating layer 26 is n-bromopropane (NPB) and has a thickness of 60 nm;
  • the film layer I27 is Liq and has a thickness of 40 nm;
  • the third transparent metal layer 28 is Al and has a thickness of 2 nm;
  • the film layer II29 is Liq and has a thickness of 40 nm.
  • the diode efficiency and brightness of the present invention are greatly improved compared with the conventional structure, and the diode efficiency with the best preparation effect can be increased from 8 Cd/A to 13 Cd/A, and the brightness can be improved by 430 Cd/m 2 . To 1260Cd/m 2 . From the cover surface luminescence analysis, since the present invention uses a double-layer transparent cathode and an outer-coupling luminescent layer, the efficiency, brightness, and the like are also greatly improved compared with the conventional structure.
  • FIG. 4 is a schematic diagram of brightness comparison between a diode prepared in one embodiment of the present invention and a conventional diode.
  • the diode A shown in the figure is a conventional diode
  • the diode B is a diode of the present invention, as can be seen from the comparison in the figure.
  • the brightness of the diode of the present invention is significantly improved compared to the conventional diode, and the voltage is also lowered.
  • the invention adopts a multilayer film encapsulation structure, that is, the barrier layer mentioned in the above embodiment to block water oxygen, and can also achieve better effects.
  • the method of using the thin film encapsulation structure of the present invention can effectively solve the pixel shrinkage problem.
  • A is a pixel shrinkage condition of a conventional diode
  • B is a diode pixel shrinkage condition in which a sandwich structure using a two-layer thin film layer and a third transparent metal layer is used as a barrier layer, and it can be seen that the diode of the present invention effectively solves the problem of pixel shrinkage.
  • the area of the non-light-emitting area is greatly reduced, so that the frame of the display device using the diode of the present invention is narrowed.
  • the diode structure of the present invention uses a composite structure in which a composite anode, a transparent metal oxide layer and a composite cathode are combined, so that the structural layers of the diode can be better matched in the energy level, and the mirror surface is added. And the micro-co-cavity effect greatly improves the luminous efficiency and brightness of the diode from the substrate surface, enhances the luminous performance and reliability of the diode, and prolongs the service life of the diode. By controlling the work function of the material of the transparent metal oxide layer to be close to the HOMO value of the hole injection layer material of the diode, the voltage of the diode can be lowered.
  • the luminescence performance of the diode from the cover surface can be further improved.
  • the barrier layer is used instead of the conventional desiccant layer, which not only reduces the non-light-emitting area of the display device, but also provides a narrow frame and a beautiful appearance.
  • the invention also provides a method for fabricating a diode.
  • the method for fabricating the diode of the present invention comprises the following steps:
  • Step S101 depositing a transparent anode layer on the glass substrate, and depositing a first transparent metal layer on the transparent anode layer;
  • a layer of ITO transparent anode layer is deposited on the glass substrate, and a thin layer of high-purity metal is deposited on the conventional single-layer ITO transparent anode layer, such as 5 to 10 nm of Ag having a purity of 99.999% or more. Au, etc., these thin metal penetration rate can reach more than 90%.
  • Step S102 depositing a transparent metal oxide layer on the first transparent metal layer
  • a thin transparent metal oxide layer is deposited on the first transparent metal layer to a thickness of 1 to 5 nm, and the work function is close to the HOMO value of the hole injection layer material.
  • the work function is close to the HOMO value of the hole injection layer material.
  • WO 3 or the like can be used.
  • Step S103 depositing a main structural layer on the transparent metal oxide layer
  • the main structural layer is a main component of the diode, and generally includes a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and The electron injecting layer is sequentially formed on the transparent metal oxide layer from bottom to top;
  • Step S104 vaporizing a composite cathode layer on the main structural layer
  • a conventional diode generally uses a very thin transparent metal layer (Mg: Ag layer) as a transparent cathode, and in the embodiment of the present invention, a multilayer laminated composite cathode layer is employed.
  • the composite cathode layer may comprise two transparent metal layers. That is, a very thin Mg:Ag metal layer and an Ag metal layer are successively evaporated in the entire light-emitting region, and each layer has a thickness of 5 nm to 15 nm, which ensures good transmittance.
  • the composite cathode layer may further comprise an opaque metal layer, and further depositing a thick metal layer on any one or several sides of the edge of the luminescent pixel, the metal thickness of the layer being greater than 50 nm, such as 50-250 nm, more preferably The thickness ranges from 60 to 90 nm, most preferably 80 nm.
  • the area of the opaque metal layer is less than one-fifth of the entire light-emitting area. This part of the cathode area is opaque, and the area of the cathode is required to be small, and most of the cathode is transparent, so as to ensure that the double-sided light-emitting effect is not affected.
  • an aluminum metal layer having a thickness of 80 nm is deposited on the two transparent metal layers.
  • the luminescent properties of the diode from the cover surface can be further improved by adding an antireflective coating layer, that is, an outcoupling luminescent layer.
  • This layer of antireflection film can be selected from lower cost organic materials, such as hole transport layer or electron transport layer material, but the selected material can not absorb too much visible light, the material needs to be stable after film formation, and crystallization cannot occur. Phenomenon and so on.
  • n-bromopropane (NPB) may be used as the material of the antireflection coating layer.
  • the thickness of the antireflection coating layer is preferably controlled to be 10 to 80 nm, more preferably 50 to 70 nm in thickness, and most preferably 60 nm.
  • the display device is obtained by attaching a desiccant in a non-light-emitting area of the diode and then encapsulating it through an NV glue, which causes an increase in the area of the non-light-emitting area of the diode, so that the frame of the display device is wider and affects the appearance.
  • the diode of the present invention further comprises a barrier layer on the anti-reflection film layer, and the barrier layer is a water-oxygen barrier film layer.
  • the barrier layer is used to replace the conventional desiccant layer and can be any film that blocks water oxygen.
  • a laminate of a plurality of film layers can generally be used as the barrier layer, and a more preferred manner is to use a sandwich structure of two film layers plus a third transparent metal layer as a barrier layer.
  • the film material used as the barrier layer may be a less expensive organic or inorganic material such as lithium quinolate (Liq) .
  • the film layers may be made of different materials or may be made of the same material.
  • the thickness of the film layer is preferably controlled to be 10 to 60 nm, and more preferably the thickness is in the range of 20 to 50 nm, and most preferably 40 nm.
  • the material of the third transparent metal layer may be a relatively inexpensive metal such as aluminum, copper or the like.
  • the thickness of the third transparent metal layer is preferably controlled to be from 1 to 10 nm, more preferably from 1-5 nm, most preferably to 2 nm.
  • the diode structure of the present invention uses a composite structure in which a composite anode, a transparent metal oxide layer and a composite cathode are combined, so that the structural layers of the diode can be better matched in the energy level, and the mirror surface is added. And the micro-co-cavity effect greatly improves the luminous efficiency and brightness of the diode from the substrate surface, enhances the luminous performance and reliability of the diode, and prolongs the service life of the diode. By controlling the work function of the material of the transparent metal oxide layer to be close to the HOMO value of the hole injection layer material of the diode, the voltage of the diode can be lowered.
  • the luminescence performance of the diode from the cover surface can be further improved.
  • the barrier layer is used instead of the conventional desiccant layer, which not only reduces the non-light-emitting area of the display device, but also provides a narrow frame and a beautiful appearance.

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Abstract

提供一种二极管及其制作方法、显示装置。其中，二极管包括：复合阳极（11），复合阳极（11）包括透明阳极层（21）和第一透明金属层（22），第一透明金属层（22）形成于透明阳极层（21）之上；透明金属氧化物层（12），透明金属氧化物层（12）形成于第一透明金属层（22）之上；主体结构层（13），主体结构层（13）形成于透明金属氧化物层（12）之上；复合阴极（14），复合阴极（14）包括两层第二透明金属层（23，24），两层第二透明金属层（23，24）形成于主体结构层（13）之上。通过上述方式，能够极大提升二极管的透光率和发光效率，增强二极管的可靠性，延长二极管的使用寿命。

Description

一种二极管及其制作方法、显示装置
【技术领域】
本发明涉及一种二极管及其制作方法、显示装置。
【背景技术】
传统的双面发光有机发光二极管通常都是在玻璃基板上依序制备单层透明阳极、有机层(包括空穴注入层、空穴传输层、发光层、电子传输层、电子注入层)，透明金属阴极以及钝化层。
这种双面发光二极管，为了能得到较好的透过率，通常将阴极做得非常薄，这样通常容易导致阴极电阻过大以及阴极与二极管周边电路接触不良，使得二极管的性能、可靠性比较差，使用寿命也不长，并且这种二极管的透过率也只有50%左右。
【发明内容】
本发明主要解决的技术问题是提供一种二极管及其制作方法、显示装置，能够极大提升二极管的透过率和发光效率，增强二极管的可靠性，延长二极管的使用寿命。
为解决上述技术问题，本发明采用的一个技术方案是：提供一种二极管，所述二极管包括：复合阳极，所述复合阳极包括透明阳极层和第一透明金属层，所述第一透明金属层形成于所述透明阳极层之上；透明金属氧化物层，所述透明金属氧化物层形成于所述第一透明金属层之上；主体结构层，所述主体结构层形成于所述透明金属氧化物层之上；复合阴极，所述复合阴极包括两层第二透明金属层，所述两层第二透明金属层形成于所述主体结构层之上。
其中，所述复合阴极还包括一层不透明金属层，所述不透明金属层形成于所述第二透明金属层的至少一条边缘上，所述不透明金属层的面积小于所述第二透明金属层面积的五分之一。
其中，所述二极管还包括增透膜层，所述增透膜层形成于所述不透明金属层之上。
其中，所述二极管还包括阻隔层，所述阻隔层形成于所述增透膜层之上，所述阻隔层为阻隔水氧的膜层。
其中，所述主体结构层包括分别依次形成于所述透明金属氧化物层之上的空穴注入层、空穴传输层、发光层、电子传输层、电子注入层。
其中，所述第一透明金属层是厚度为5-10nm的金或银金属层。
其中，所述透明金属氧化物层的厚度为1-5nm，所述金属氧化物的功函数与所述二极管的电子注入层材料的最高已占轨道值的差值为0~1eV。
其中，所述金属氧化物的功函数与所述二极管的电子注入层材料的最高已占轨道值的差值为0eV。
其中，所述两层第二透明金属层分别是厚度为5-15nm的镁金属层和镁、银金属层，所述不透明金属层是厚度为50-250nm的铝金属层。
其中，所述增透膜层的材料为用作所述二极管的空穴传输层材料或电子传输层材料。
其中，所述增透膜层是厚度为10-80nm的正溴丙烷层。
为解决上述技术问题，本发明的提供的另一个技术方案是，提供一种显示装置，包括上述的二极管以及盖板。
为解决上述技术问题，本发明采用的还有一个技术方案是：提供一种二极管的制作方法，包括：在玻璃基板上蒸镀一层透明阳极层，在所述透明阳极之上蒸镀一第一透明金属层，所述透明阳极层、所述第一透明金属层构成一个复合阳极；在所第一透明金属层上蒸镀一层透明金属氧化物层；在所述透明金属氧化物层上蒸镀主体机构层；在所述主体结构层上先后蒸镀两层第二透明金属层。
其中，所述在所述主体结构层上先后蒸镀两层第二透明金属层的步骤之后，还包括：在所述第二透明金属层的至少一条边缘之上蒸镀一层不透明金属层，所述不透明金属层的面积小于所述第二透明金属层面积的五分之一。
其中，所述在所述第二透明金属层的至少一条边缘之上蒸镀一层不透明金属层的步骤之后，还包括：在所述不透明金属层之上蒸镀一层增透膜层。
其中，所述在所述不透明金属层之上蒸镀一层增透膜层的步骤之后，还包括：在所述增透膜层之上覆盖阻隔层，所述阻隔层为阻隔水氧的膜层。
其中，所述阻隔层包括一个第三透明金属层与两个薄膜层，所述第三透明金属层形成于两个薄膜层之间。
其中，所述增透膜层的材料为用作所述二极管的空穴传输层材料或电子传输层材料。
本发明的有益效果是：区别于现有技术的情况，本发明二极管结构使用复合阳极、透明金属氧化物层和复合阴极相结合的复合结构，能够使得二极管的各结构层在能级匹配上更好，加上镜面及微共腔效应，极大提升二极管从基板面的发光效率和亮度，增强二极管的发光性能和可靠性，延长二极管的使用寿命。
【附图说明】
图1是本发明二极管一个实施方式的结构示意图；
图2是本发明二极管另一个实施方式的结构示意图；
图3是本发明显示装置一个实施方式的结构示意图；
图4是本发明二极管的亮度对比示意图；
图5是本发明二极管的像素收缩效果对比示意图；
图6是本发明二极管的制作方法一个实施方式的流程图。
【具体实施方式】
参阅图1，本发明二极管一个实施方式包括复合阳极11、透明金属氧化物层12、主体结构层13以及复合阴极14，为了进一步阐述本发明二极管的结构，请结合参阅图2：
复合阳极11包括透明阳极层21和第一透明金属层22，第一透明金属层22形成于透明阳极层21之上，该第一透明金属层22为厚度很薄的高纯度金属层，厚度控制在能实现透明效果，且穿透率能达到90%以上。比如可以在传统透明阳极层21之上通过蒸镀一层厚度在5-10nm的纯度在99.999%以上的金或银金属层作为第一透明金属层22。比如以10nm厚度的银金属层作为第一透明金属层22。
透明金属氧化物层12形成于第一透明金属层22之上。透明金属氧化物层12的厚度宜控制在1-5nm之间。为了降低二极管电压，可以选用功函数与二极管的空穴注入层材料最高已占轨道(HOMO)值接近(差值范围0-1eV)的材料作为金属氧化物层12的材料，最好选用功函数与二极管的空穴注入层材料HOMO值相同的材料作为金属氧化物层12的材料。比如可以选用WO 3 作为金属氧化物层的材料。
主体结构层13形成于透明金属氧化物层12之上，主体结构层13是二极管构成的主要组成部分，通常包括空穴注入层、空穴传输层、发光层、电子传输层以及电子注入层，其中空穴注入层、空穴传输层、发光层、电子传输层以及电子注入层分别依次形成于透明金属氧化物层12之上。
复合阴极14包括两个第二透明金属层，分别为第二透明金属层Ⅰ23、第二透明金属层Ⅱ24，第二透明金属层Ⅰ23、第二透明金属层Ⅱ24分别依次形成于主体结构层13之上，即直接形成于电子注入层之上。
为进一步提升二极管的发光效果，复合阴极还进一步包括一不透明金属层25，不透明金属层25形成于第二透明金属层Ⅱ24的至少一条边缘上，面积小于第二透明金属层Ⅱ24面积的五分之一。通常，在整个发光区域全部蒸镀一层第二透明金属层Ⅰ23，在第二透明金属层Ⅰ23之上蒸镀一层第二透明金属层Ⅱ24，其中第二透明金属层23和第二透明金属层Ⅱ24可以分别是厚度为5-15nm的镁(Mg):银(Ag)金属层以及银(Ag)金属层，保证具有较好的透过率。然后在第二透明金属层Ⅱ24的任意一条或几条边再蒸镀一层比较厚的不透明金属层25，该不透明金属层25的厚度大于50nm，比如50-250nm的金属铝层，较优选的厚度范围为60-90nm，最优选为80nm。该不透明金属层25部分不透光，其他部分阴极都是透明的，能够保证本发明二极管的双面发光效果。
通过复合阳极、透明金属氧化物层以及复合阴极的结合，使得二极管在能级匹配上更好，加上镜面及微共腔效应，二极管的效率和亮度都比传统结构二极管有较大提高。
进一步地，本发明的二极管还包括一增透膜层26，该增透膜层26形成于不透明金属层25之上，为外耦合发光层，能够进一步提高二极管的发光性能。该增透膜层26可以选用成本较低的有机材料，比如用作二极管空穴传输层或电子传输层的材料，但是所选材料不宜对可见光有较大的吸收，成膜后材料应该较稳定，不会出现结晶化现象等。比如可以选用正溴丙烷(NPB)作为增透膜层26的材料，增透膜层26的厚度宜控制在10-80nm，较优选厚度范围为50-70nm，最优选的厚度范围为60nm。
通常情况下，显示装置都是通过在二极管的非发光区域贴干燥剂然后通过NV胶封装得到，这样会导致二极管非发光区面积增大，使得显示设备的边框较宽，影响美观。
为使将二极管封装得到的显示装置更加美观，进一步地，本发明的二极管还包括一阻隔层，该阻隔层为阻隔水氧的膜层。该阻隔层用于替代传统的干燥剂层，可以是任何有阻隔水氧作用的薄膜。为了达到较好的阻隔效果，通常可以采用多个薄膜层的叠层来作为阻隔层，更优选的方式为采用两个薄膜层即薄膜层Ⅰ27、薄膜层Ⅱ29加第三透明金属层28的夹层结构作为阻隔层(图示结构中标号为27、28、29的结构层共同构成阻隔层)。
用作阻隔层的薄膜材料可以是价格较低的有机或无机材料，比如8-羟基喹啉锂(Liq) 。薄膜层Ⅰ27以及薄膜层Ⅱ29可以分别采用不同的材料，也可以采用相同的材料制备。薄膜层Ⅰ27、薄膜层Ⅱ29的厚度宜控制在10-60nm，较优选的厚度范围为20-50nm，最优选为40nm。
第三透明金属层28的材料可以采用较便宜的金属，比如铝、铜等。第三透明金属层28的厚度宜控制在1-10nm，较优选厚度范围为1-5nm，最优选为2nm。
本发明进一步提供一种显示装置的实施方式，请参阅图3，为本发明显示装置一个实施方式的结构示意图，其中：
显示装置包括玻璃基板31、二极管32以及盖板33，二极管32形成于玻璃基板31之上，该二极管32可以是上述任一实施方式提到的二极管，二极管32通过UV胶或FRIT胶34与盖板33进行封装形成显示装置。采用本发明实施方式中的二极管封装得到的显示装置边框窄，外形美观。
本发明其中一个实施方式中制备的二极管各个结构层的参数如下：
透明阳极层21为ITO；
第一透明金属层22为Ag，纯度99.999%，厚度为10nm；
透明金属氧化物层12为WO 3 ，HOMO为5.7eV，与空穴注入层或者传输层的HOMO5.3eV/5.4eV接近；
主体结构层13为空穴注入层/空穴传输层/发光层/电子传输层/电子注入层(HIL/HTL/EML/ETL/EIL)；
第二透明金属层Ⅰ23为Mg:Ag，厚度为10nm；
第二透明金属层Ⅱ24为Ag，厚度为10nm；
不透明金属层25为Al，厚度为80nm；
增透膜层26为正溴丙烷(NPB)，厚度为60nm;
薄膜层Ⅰ27为Liq，厚度为40nm；
第三透明金属层28为Al，厚度为2nm；
薄膜层Ⅱ29为Liq，厚度为40nm。
对于上述二极管从基板面发光分析，本发明的二极管效率和亮度均比传统结构有大幅度提升，制备的效果最好的二极管效率可由8Cd/A增加到13Cd/A，亮度可由430Cd/m 2 提升到1260Cd/m 2 。从盖板面发光分析，由于本发明使用双层透明阴极和外耦合发光层，比传统结构在效率、亮度等也均大幅提升。
请参阅图4，本发明其中一个实施方式中制备得到的二极管与传统二极管的亮度对比示意图，其中，图中所示二极管A为传统的二极管，二极管B为本发明的二极管，由图中对比可知，本发明的二极管相对于传统二极管亮度有明显提升，电压也有所下降。
本发明采用多层薄膜封装结构即上述实施方式中提到的阻隔层来阻绝水氧，也能达到比较好的效果。请参阅图5，本发明的采用薄膜封装结构的方式能够有效的解决像素收缩问题。图中A为传统二极管的像素收缩情况，B为本发明的采用两层薄膜层加第三透明金属层的夹层结构作为阻隔层的二极管像素收缩情况，可见本发明二极管有效解决了像素收缩问题，极大的减少了非发光区的面积，使得采用本发明二极管的显示装置的边框变窄。
通过上述实施方式的阐述，可以理解，本发明二极管结构使用复合阳极、透明金属氧化物层和复合阴极相结合的复合结构，能够使得二极管的各结构层在能级匹配上更好，加上镜面及微共腔效应，极大提升二极管从基板面的发光效率和亮度，增强二极管的发光性能和可靠性，延长二极管的使用寿命。通过，通过控制透明金属氧化物层的材料的功函数与二极管的空穴注入层材料的HOMO值相接近，能够降低二极管的电压。
通过在二极管的阴极之后再增设一层增透膜层，能够进一步提高二极管从盖板面的发光性能。
另一方面，将本发明的二极管封装成显示装置时，通过阻隔层来代替传统的干燥剂层，不仅能减少显示装置的非发光区面积，而且封装得到的显示装置边框窄，外形比较美观。
本发明还提供一种二极管的制作方法，请参阅图6，本发明二极管的制作方法包括以下步骤：
步骤S101：在玻璃基板上蒸镀一层透明阳极层，在透明阳极层之上蒸镀一第一透明金属层；
在玻璃基板上蒸镀一层ITO透明阳极层，在传统的单层ITO透明阳极层之上，蒸镀一层厚度很薄的高纯度金属，如5~10nm的纯度在99.999%以上的Ag、Au等，这些薄得金属穿透率可达到90%以上。
步骤S102：在第一透明金属层之上蒸镀一层透明金属氧化物层；
第一透明金属层之上再蒸镀一层薄的透明金属氧化物层，厚度在1~5nm，功函数与空穴注入层材料HOMO值接近。比如可以采用WO 3 等。
步骤S103：在透明金属氧化物层上蒸镀主体结构层；
主体结构层是二极管的主要组成部分，通常包括空穴注入层、空穴传输层、发光层、电子传输层以及电子注入层，空穴注入层、空穴传输层、发光层、电子传输层以及电子注入层依次从下往上形成于透明金属氧化物层上；
步骤S104：在主体结构层上蒸镀复合阴极层；
传统的二极管通常使用一层很薄的透明金属层(Mg：Ag层)作为透明阴极，而本发明实施方式中采用多层叠层的复合阴极层。其中，复合阴极层可以包括两层透明金属层。即在整个发光区全部先后蒸镀上很薄的Mg:Ag金属层和Ag金属层，每一层的厚度在5nm~15nm之间，保证具有良好的透过率。
复合阴极层还可以进一步包括一不透明金属层，在发光像素边缘的任意一条或几条边再蒸镀一层膜厚较厚的金属层，此层金属厚度大于50nm，比如50-250nm，较优选的厚度范围为60-90nm，最优选为80nm。不透明金属层面积小于整个发光面积的五分之一，这部分阴极面积不透光，要求这部分阴极的面积小，大部分阴极是透明的，保证不影响双面发光效果。比如在两层透明金属层之上蒸镀一层厚度为80nm的铝金属层。
在阴极之后，可以通过增加一层增透膜层即外耦合发光层进一步提高二极管从盖板面的发光性能。这一层增透膜可以选用成本较低的有机材料，比如空穴传输层或电子传输层材料，但是所选的材料不能对可见光有过大吸收，成膜后材料需要稳定，不能出现结晶化现象等。比如可以选用正溴丙烷(NPB)作为增透膜层的材料，增透膜层的厚度宜控制在10-80nm，较优选厚度范围为50-70nm，最优选的厚度范围为60nm。
通常情况下，显示装置都是通过在二极管的非发光区域贴干燥剂然后通过NV胶封装得到，这样会导致二极管非发光区面积增大，使得显示设备的边框较宽，影响美观。
为使将二极管封装得到的显示装置更加美观，进一步地，本发明的二极管在上述增透膜层之上还包括一阻隔层，该阻隔层为阻隔水氧的膜层。该阻隔层用于替代传统的干燥剂层，可以是任何有阻隔水氧作用的薄膜。为了达到较好的阻隔效果，通常可以采用多个薄膜层的叠层来作为阻隔层，更优选的方式为采用两个薄膜层加第三透明金属层的夹层结构作为阻隔层。
用作阻隔层的薄膜材料可以是价格较低的有机或无机材料，比如8-羟基喹啉锂(Liq) 。薄膜层可以分别采用不同的材料，也可以采用相同的材料制备。薄膜层的厚度宜控制在10-60nm，较优选的厚度范围为20-50nm，最优选为40nm。
第三透明金属层的材料可以采用较便宜的金属，比如铝、铜等。第三透明金属层的厚度宜控制在1-10nm，较优选厚度范围为1-5nm，最优选为2nm。
通过上述实施方式的阐述，可以理解，本发明二极管结构使用复合阳极、透明金属氧化物层和复合阴极相结合的复合结构，能够使得二极管的各结构层在能级匹配上更好，加上镜面及微共腔效应，极大提升二极管从基板面的发光效率和亮度，增强二极管的发光性能和可靠性，延长二极管的使用寿命。通过，通过控制透明金属氧化物层的材料的功函数与二极管的空穴注入层材料的HOMO值相接近，能够降低二极管的电压。
通过在二极管的阴极之后再增设一层增透膜层，能够进一步提高二极管从盖板面的发光性能。
另一方面，将本发明的二极管封装成显示装置时，通过阻隔层来代替传统的干燥剂层，不仅能减少显示装置的非发光区面积，而且封装得到的显示装置边框窄，外形比较美观。
以上所述仅为本发明的实施方式，并非因此限制本发明的专利范围，凡是利用本发明说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。

Claims (18)

  1. 一种二极管，其中，包括：
    复合阳极，所述复合阳极包括透明阳极层和第一透明金属层，所述第一透明金属层形成于所述透明阳极层之上；
    透明金属氧化物层，所述透明金属氧化物层形成于所述第一透明金属层之上；
    主体结构层，所述主体结构层包括依次形成于所述透明金属氧化物层之上的空穴注入层、空穴传输层、发光层、电子传输层、电子注入层；
    复合阴极，所述复合阴极包括两层第二透明金属层和一层不透明金属层，所述两层第二透明金属层形成于所述主体结构层之上，所述不透明金属层形成于所述第二透明金属层的至少一条边缘上，所述不透明金属层的面积小于所述第二透明金属层面积的五分之一。
  2. 根据权利要求1所述的二极管，其中，
    所述二极管还包括增透膜层，所述增透膜层形成于所述不透明金属层之上。
  3. 根据权利要求2所述的二极管，其特征在于，
    所述二极管还包括阻隔层，所述阻隔层形成于所述增透膜层之上，所述阻隔层为阻隔水氧的膜层。
  4. 根据权利要求1所述的二极管，其中，
    所述第一透明金属层是厚度为5-10nm的金或银金属层。
  5. 根据权利要求1所述的二极管，其中，
    所述透明金属氧化物层的厚度为1-5nm，所述金属氧化物的功函数与所述二极管的电子注入层材料的最高已占轨道值的差值为0~1eV。
  6. 根据权利要求5所述的二极管，其中，
    所述金属氧化物的功函数与所述二极管的电子注入层材料的最高已占轨道值的差值为0eV。
  7. 根据权利要求1所述的二极管，其中，
    所述两层第二透明金属层分别是厚度为5-15nm的镁金属层和镁、银金属层，所述不透明金属层是厚度为50-250nm的铝金属层。
  8. 根据权利要求3所述的二极管，其中，
    所述阻隔层包括一个第三透明金属层与两个薄膜层，所述第三透明金属层形成于所述两个薄膜层之间。
  9. 根据权利要求8所述的二极管，其中，
    所述两个薄膜层是厚度为10-60nm的8-羟基喹啉锂的膜层，所述第三透明金属层是厚度为1-10nm的铝金属层。
  10. 根据权利要求2所述的二极管，其中，
    所述增透膜层的材料为用作所述二极管的空穴传输层材料或电子传输层材料。
  11. 根据权利要求10所述的二极管，其中，
    所述增透膜层是厚度为10-80nm的正溴丙烷层。
  12. 一种显示装置，其中，包括二极管以及盖板，所述二极管包括：
    复合阳极，所述复合阳极包括透明阳极层和第一透明金属层，所述第一透明金属层形成于所述透明阳极层之上；
    透明金属氧化物层，所述透明金属氧化物层形成于所述第一透明金属层之上；
    主体结构层，所述主体结构层包括依次形成于所述透明金属氧化物层之上的空穴注入层、空穴传输层、发光层、电子传输层、电子注入层；
    复合阴极，所述复合阴极包括两层第二透明金属层和一层不透明金属层，所述两层第二透明金属层形成于所述主体结构层之上，所述不透明金属层形成于所述第二透明金属层的至少一条边缘上，所述不透明金属层的面积小于所述第二透明金属层面积的五分之一。
  13. 根据权利要求12所述的显示装置，其中，
    所述二极管还包括增透膜层，所述增透膜层形成于所述不透明金属层之上。
  14. 根据权利要求13所述的显示装置，其中，
    所述二极管还包括阻隔层，所述阻隔层形成于所述增透膜层之上，所述阻隔层为阻隔水氧的膜层。
  15. 一种二极管的制作方法，其中，包括：
    在玻璃基板上蒸镀一层透明阳极层，在所述透明阳极之上蒸镀一第一透明金属层，所述透明阳极层、所述第一透明金属层构成一个复合阳极；
    在所第一透明金属层上蒸镀一层透明金属氧化物层；
    在所述透明金属氧化物层上蒸镀主体机构层；
    在所述主体结构层上先后蒸镀两层第二透明金属层。
  16. 根据权利要求15所述的方法，其中，
    所述在所述主体结构层上先后蒸镀两层第二透明金属层的步骤之后，还包括：在所述第二透明金属层的至少一条边缘之上蒸镀一层不透明金属层，所述不透明金属层的面积小于所述第二透明金属层面积的五分之一。
  17. 根据权利要求16所述的方法，其中，
    所述在所述第二透明金属层的至少一条边缘之上蒸镀一层不透明金属层的步骤之后，还包括：在所述不透明金属层之上蒸镀一层增透膜层。
  18. 根据权利要求17所述的方法，其中，
    所述在所述不透明金属层之上蒸镀一层增透膜层的步骤之后，还包括：在所述增透膜层之上覆盖阻隔层，所述阻隔层为阻隔水氧的膜层。
PCT/CN2013/072488 2013-03-07 2013-03-12 一种二极管及其制作方法、显示装置 Ceased WO2014134839A1 (zh)

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