(19)
(11)EP 2 768 040 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
03.08.2022 Bulletin 2022/31

(21)Application number: 14151397.8

(22)Date of filing:  16.01.2014
(51)International Patent Classification (IPC): 
H01L 51/52(2006.01)
H01L 27/32(2006.01)
H01L 51/56(2006.01)
(52)Cooperative Patent Classification (CPC):
H01L 51/5256; H01L 27/32; H01L 51/56

(54)

Organic electroluminescent device having thin film encapsulation structure and method of fabricating the same

Organische elektrolumineszierende Vorrichtung mit Dünnschichtverkapselung und deren Herstellungsmethode

Dispositif électroluminescent organique avec encapsulation à film mince et sa méthode de fabrication


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 14.02.2013 KR 20130016057

(43)Date of publication of application:
20.08.2014 Bulletin 2014/34

(60)Divisional application:
22182359.4

(73)Proprietor: Samsung Display Co., Ltd.
Gyeonggi-do (KR)

(72)Inventors:
  • Oh, Min-Ho
    Gyunggi-Do (KR)
  • Cho, Yoon-Hyeung
    Gyunggi-Do (KR)
  • Kim, Yong-Tak
    Gyunggi-Do (KR)
  • Lee, So-Young
    Gyunggi-Do (KR)
  • Kim, Jong-Woo
    Gyunggi-Do (KR)
  • Moon, Ji-Young
    Gyunggi-Do (KR)

(74)Representative: Taor, Simon Edward William et al
Venner Shipley LLP 200 Aldersgate
London EC1A 4HD
London EC1A 4HD (GB)


(56)References cited: : 
WO-A1-2013/018761
US-A1- 2004 229 051
KR-B1- 101 218 651
US-A1- 2006 022 219
  
  • Anonymous: "Shin-Etsu Silicone : Silane coupling agents", , 25 September 2017 (2017-09-25), XP055409372, Retrieved from the Internet: URL:https://www.shinetsusilicone-global.co m/products/type/silanecoup/index.shtml [retrieved on 2017-09-25]
  
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description


[0001] The present invention generally relates to an organic electroluminescent device having a thin film encapsulation structure, and more particularly, to an organic electroluminescent device having a thin film encapsulation structure, in which an inorganic layer and an organic layer are stacked, and a method of fabricating the same.

[0002] Encapsulation technology of an organic light-emitting device may include substrate bonding technology for bonding an encapsulation substrate and a substrate having an organic light-emitting device formed thereon to each other, and a thin film encapsulation technology for forming an encapsulation layer in the form of a thin film without an encapsulation substrate. The bonding of the encapsulation substrate and the substrate having an organic light-emitting device formed thereon is performed by using an inorganic frit or an organic adhesive. An inorganic layer, such as AlOx, SiNx, SiOx, and SiON, on a panel may be used for thin film encapsulation.

[0003] EP 2740547 A1 discloses a functional film being organically and inorganically laminated to have a desired function such as high gas barrier performance and having high adhesiveness between inorganic and organic layers.

[0004] An inorganic layer for thin film encapsulation is thin, but a density thereof is high, and thus, the inorganic layer for thin film encapsulation may have barrier characteristics with respect to moisture and oxygen. However, since an inorganic layer has brittle characteristics, mechanical properties thereof under stress may be poor. In particular, a plurality of particles may exist on a substrate during a process of fabricating an organic light-emitting device, and an inorganic layer disposed on the particles may be significantly affected by stress, and thus, the barrier characteristics of the inorganic layer may be degraded.

[0005] Therefore, a structure is introduced for planarizing an irregular surface, such as particles, by introducing an organic layer between the inorganic layers as well as relieving the stress of the inorganic layer. For example, acryl, silicone, and epoxy can be used as the organic layer.

[0006] In general, thermal stability must be maintained at about 100°C for the reliability of the organic light-emitting device. However, a phenomenon of peeling-off of an interface between the inorganic layer and the organic layer may occur during exposure at a high temperature for a prolonged period of time. For example, since strong chemical bonding may be difficult to be formed in the case where an acryl layer is deposited on a SiNx layer deposited through a plasma enhanced chemical vapor deposition (PECVD) process, an interface between the SiNx layer and the acryl layer may be peeled off due to heat.

[0007] The present invention provides an organic light-emitting device having a stable thin film encapsulation structure by improving interfacial adhesion between an inorganic layer and an organic layer, and a method of fabricating the same.

[0008] According to an aspect of the invention, there is provided an organic electroluminescent display device as set out in claim 1. Preferred features of this aspect are set out in claims 2 to 8.

[0009] According to an aspect of the invention, there is provided a method of fabricating an organic electroluminescent display device as set out in claim 9. Preferred features of this aspect are set out in claims 10 to 15.

[0010] The above and other features and advantages of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings in which:

FIG. 1 is a cross-sectional view schematically illustrating an organic electroluminescent display device constructed as an embodiment according to an embodiment of the present invention; and

FIG. 2 is a diagram conceptually illustrating a process in which an intermediate layer forms a bond between an inorganic layer and an organic layer.



[0011] Hereinafter, the present invention will be described more fully with reference to the accompanying drawings, in which exemplary embodiments of the invention are shown. The invention may, however, be embodied in many different forms and should not be construed as being 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 the invention to those of ordinary skill in the art. In the drawings, the thicknesses of layers and regions are exaggerated for clarity. Like reference numerals refer to like elements throughout.

[0012] As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. Expressions such as "at least one of," when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list.

[0013] FIG. 1 is a cross-sectional view schematically illustrating an organic electroluminescent display device constructed as an embodiment according to an embodiment of the present invention.

[0014] An organic electroluminescent display device 100 constructed as an embodiment according to the principles of the present invention includes a substrate 10, an organic light-emitting device 20 on the substrate 10, and an encapsulation layer 30 formed on the substrate 10 to cover the organic light-emitting device 20.

[0015] Substrates formed of various materials, such as glass, plastic, silicon, or metal, may be used as the substrate 10. A buffer layer (not shown) for preventing diffusion of impurity elements or ions and infiltration of moisture from the substrate 10 to a thin film transistor (TFT) or the organic light-emitting device 20 on the substrate 10 and for planarizing a surface of the substrate 10 may be formed on a top surface of the substrate 10. Also, a TFT (not shown), as a circuit for driving the organic light-emitting device 20, is formed on the substrate 10.

[0016] The organic light-emitting device 20 includes a first electrode 21, a second electrode 23, and an organic layer 22 between the first electrode 21 and the second electrode 23.

[0017] The first electrode 21 may be an anode, and in this case, the first electrode 21 may be selected from materials having a high work function so as to facilitate hole injection. The first electrode 21 may be a transmissive electrode or a reflective electrode. The first electrode 21, for example, may be formed of indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), aluminum (Al)-doped zinc oxide (AZO), indium oxide (In2O3), or tin oxide (SnO2). The first electrode 21 may also be formed as a reflective electrode by using magnesium (Mg), silver (Ag), Al, aluminum-lithium (Al-Li), calcium (Ca), Ag-ITO, Mg-In, or Mg-Ag. The first electrode 21 may have a single layer structure or a multilayer structure having two or more layers. For example, the first electrode 21 may have a three-layer structure of ITO/Ag/ITO, but the first electrode 21 is not limited thereto in embodiments of the invention.

[0018] The organic layer 22 in the organic light-emitting device 20 includes at least an emissive layer (EML) and in addition, may further include layers for hole injection and transport, electron injection and transport, and charge balance.

[0019] The second electrode 23 may be a cathode, and in this case, a metal, an alloy, an electrically conductive compound, or a mixture of two or more thereof having a low work function may be used as the second electrode 23. The second electrode 23, for example, may be included as a transparent electrode or a reflective electrode. In the case that the second electrode 23 is included as a transparent electrode, the second electrode 23 may include a thin film formed of Li, Ca, Al, Mg, Mg-In, Mg-Ag, LiF-Al, LiF-Ca, or a compound thereof and an auxiliary electrode formed of a transparent conductive material, such as ITO, IZO, ZnO, or In2O3, disposed thereon. Alternatively, in the case that the second electrode 23 is included as a reflective electrode, the second electrode 23 may be formed of Li, Ca, Al, Mg, Mg-In, Mg-Ag, LiF-Al, LiF-Ca, or a compound thereof.

[0020] The encapsulation layer 30 is composed of an inorganic layer 31 and an organic layer 33 alternatingly stacked with an intermediate layer 32 between the inorganic layer 31 and the organic layer 33.

[0021] The inorganic layer 31, for example, may be formed of silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, aluminum nitride, aluminum oxynitride, titanium oxide, titanium nitride, tantalum oxide, tantalum nitride, hafnium oxide, hafnium nitride, zirconium oxide, zirconium nitride, cerium oxide, cerium nitride, tin oxide, tin nitride, or magnesium oxide. An optimum thickness of the inorganic layer 31 may be determined according to productivity or device characteristics. The inorganic layer 31 is thin, but a density thereof is high, and thus, the inorganic layer 31 may have barrier characteristics with respect to moisture and oxygen.

[0022] The organic layer 33 may be formed of an acryl-based resin, a methacryl-based resin, an isoprene-based resin, a vinyl-based resin, an epoxy-based resin, a urethane-based resin, a cellulose-based resin, a perylene-based resin, an imide-based resin, or a mixture of two or more thereof. An optimum thickness of the organic layer 33 may be determined according to characteristics of the inorganic layer 31, productivity, and device characteristics. The organic layer 33 may act to relieve stress of the inorganic layer 31 and planarize the inorganic layer 31.

[0023] One surface of the intermediate layer 32 is bonded to the inorganic layer 31 through bonding sites on a surface of the inorganic layer 31, and another surface of the intermediate layer 32 is boned to the organic layer 33 by polymerization. The intermediate layer 32 is formed of a material which is bonded to a bonding site, such as oxygen, on the surface of the inorganic layer 31 and is bonded to the organic layer 33 by polymerization. The intermediate layer 32 is formed of a monomer which is an organic compound which may include a polymerizable double bond. For example, the intermediate layer 32 may be formed of methacrylate, acrylate, or epoxy. For example, a hydroxyl or carbonyl moiety of methacrylate may be bonded to a bonding site, e.g., an oxygen or hydrogen atom, on the surface of the inorganic layer 31 and/or a carbonyl or carbon-carbon double bond moiety thereof may be bonded to the organic layer 33 by polymerization. An optimum thickness of the intermediate layer 32 may be determined according to a degree of adhesion between the inorganic layer 31 and the organic layer 33. For example, the intermediate layer 32 may be formed to a thickness of a few nanometres (few tens of angstrom (Å)), but the thickness of the intermediate layer 32 is not limited thereto in embodiments of the invention.

[0024] In the encapsulation layer 30, the pluralities of organic layers 33 and inorganic layers 31 may be alternatingly stacked and the intermediate layer 32 may be disposed between the organic layer 33 and the inorganic layer 31.

[0025] Since the intermediate layer 32 is bonded to the organic layer 33 and the inorganic layer 31, adhesion between the organic layer 33 and the inorganic layer 31 is improved, and thus, occurrence of peeling-off due to thermal stress and deformation may be prevented.

[0026] Hereinafter, a method of fabricating an organic electroluminescent display device according to an embodiment of the present invention will be described.

[0027] First, a substrate 10 is provided. Substrates formed of various materials, such as glass, plastic, silicon, or metal, may be used as the substrate 10. A buffer layer (not shown) for preventing diffusion of impurity elements or ions and infiltration of moisture from the substrate 10 to a TFT or an organic light-emitting device 20 above the substrate 10 and for planarizing a surface of the substrate 10 may be formed on a top surface of the substrate 10. Also, a TFT (not shown), as a circuit for driving the organic light-emitting device 20, is formed on the substrate 10.

[0028] The organic light-emitting device 20 electrically connected to the TFT (not shown) is formed on the substrate 10. The organic light-emitting device 20 includes a first electrode 21, a second electrode 23, and an organic layer 22 between the first electrode 21 and the second electrode 23.

[0029] The first electrode 21 may be an anode, and in this case, the first electrode 21 may be formed by selecting a material having a high work function so as to facilitate hole injection. The first electrode 21 may be a transmissive electrode or a reflective electrode. The first electrode 21, for example, may be formed of ITO, IZO, ZnO, AZO, In2O3, or SnO2. The first electrode 21 may also be formed as a reflective electrode by using Mg, Ag, Al, Al-Li, Ca, Ag-ITO, Mg-In, or Mg-Ag. The first electrode 21 may be formed as a single layer structure or a multilayer structure having two or more layers. The first electrode 21 may be formed by evaporation or sputtering.

[0030] The organic layer 22 includes at least an EML and in addition, may further include a hole injection layer (HIL), a hole transport layer (HTL), an electron transport layer (ETL), and an electron injection layer (EIL). The organic layer 22 may be formed of a low molecular weight or high molecular weight material, and may be formed by using various methods, such as a vacuum deposition method, a spin coating method, a casting method, and a Langmuir-Blodgett (LB) method.

[0031] The hole injection layer may be formed of a phthalocyanine compound, such as copper phthalocyanine, N,N'-diphenyl-N,N'-bis-[4-(phenyl-m-tolyl-amino)-phenyl]-biphenyl-4,4'-diamine (DNTPD), 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine (m-MTDATA), 4,4',4"-Tris(N,N-diphenylamino)triphenylamine (TDATA), 4,4',4"-tris{N,-(2-naphthyl)-N-phenylamino}-triphenylamine (2T-NATA), poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS), polyaniline/dodecylbenzenesulfonic acid (PANI/DBSA), polyaniline/camphor sulfonic acid (PANI/CSA), or polyaniline/poly(4-styrenesulfonate) (PANI/PSS). However, the hole injection layer is not limited thereto in embodiments of the invention.

[0032] The hole transport layer may be formed of a carbazole derivative, such as N-phenylcarbazole and polyvinylcarbazole, and a triphenylamine-based material such as N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4'-diamine (TPD), N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine (NPB), or 4,4',4"-tris(N-carbazolyl)triphenylamine (TCTA). However, the hole transport layer is not limited thereto in embodiments of the invention.

[0033] The electron transport layer may be formed of Alq3, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 4,7-diphenyl-1,10-phenanthroline (Bphen), 3-(4-Biphenylyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole (TAZ), 4-(Naphthalen-1-yl)-3,5-diphenyl-4H-1,2,4-triazole (NTAZ), 2-(4-Biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (tBu-PBD), Bis(2-methyl-8-quinolinolato-N1,O8)-(1,1'-Biphenyl-4-olato)aluminum (BAlq), beryllium bis(benzoquinolin-10-olate) (Bebq2), or 9,10-di(naphthalene-2-yl)anthracene (ADN). However, the electron transport layer is not limited thereto in embodiments of the invention.

[0034] The electron injection layer may be formed by using a material such as LiF, NaCl, CsF, Li2O, BaO, and Liq.

[0035] The emissive layer may be formed to include a host material and a dopant material.

[0036] Examples of the host may be tris-(8-quinolinolato)aluminum (Alq3), 4,4'-bis(N-carbazolyl)-1,1'-biphenyl (CBP), poly(n-vinylcabazole) (PVK), ADN, TCTA, 1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene (TPBI), 3-tert-butyl-9,10-di(naphtha-2-yl)anthracene (TBADN), distyrylarylene (DSA), E3, or 4,4'-bis(9-carbazolyl)-2,2'-dimethyl-biphenyl (CDBP). However, the host is not limited thereto in embodiments of the invention.

[0037] Examples of the dopant may be Pt(II) octaethylporphine (PtOEP), tris(2-phenylisoquinoline)iridium (Ir(piq)3), bis(2-(2'-benzothienyl)-pyridinato-N,C3')iridium(acetylacetonate) (Btp2Ir(acac)), tris(2-phenylpyridine)iridium (Ir(ppy)3), Bis(2-phenylpyridine)(Acetylacetonato)iridium(III) (Ir(ppy)2(acac)), tris(2-(4-tolyl)phenylpyridine)iridium (Ir(mppy)3), 10-(2-benzothiazolyl)-1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H,11H-[1]benzopyrano[6,7,8-ij]- quinolizin-11-one (C545T), Bis[3,5-difluoro-2-(2-pyridyl)phenyl](picolinato)iridium(III) (F2Irpic), (F2ppy)2Ir(tmd), Ir(dfppz)3, 4,4'-bis(2,2'-diphenylethen-1-yl)biphenyl (DPVBi), 4,4'-bis[4-(diphenylamino)styryl]biphenyl (DPAVBi), or 2,5,8,11-tetra-tert-butyl perylene (TBPe). However, the dopant is not limited thereto in embodiments of the invention.

[0038] The second electrode 23 may be a cathode, and in this case, the second electrode 23 may be formed by using a metal, an alloy, an electrically conductive compound, or a mixture of two or more thereof having a low work function. The second electrode 23, for example, may be formed as a transparent electrode or a reflective electrode. In the case that the second electrode 23 is a transparent electrode, the second electrode 23 may be formed as a thin film formed of Li, Ca, Al, Mg, Mg-In, Mg-Ag, LiF-Al, LiF-Ca, or a compound thereof and an auxiliary electrode formed of a transparent conductive material, such as ITO, IZO, ZnO, or In2O3, disposed thereon. Alternatively, in the case where the second electrode 23 is a reflective electrode, the second electrode 23, for example, may be formed of Li, Ca, Al, Mg, Mg-In, Mg-Ag, LiF-Al, LiF-Ca, or a compound thereof. The second electrode 23 may be formed by sputtering or vacuum deposition.

[0039] An encapsulation layer 30 is formed on the organic light-emitting device 20.

[0040] The encapsulation layer 30 is composed of an inorganic layer 31 and an organic layer 33 alternatingly stacked with an intermediate layer 32 between the inorganic layer 31 and the organic layer 33.

[0041] The inorganic layer 31, for example, may be formed of silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, aluminum nitride, aluminum oxynitride, titanium oxide, titanium nitride, tantalum oxide, tantalum nitride, hafnium oxide, hafnium nitride, zirconium oxide, zirconium nitride, cerium oxide, cerium nitride, tin oxide, tin nitride, or magnesium oxide. An optimum thickness of the inorganic layer 31 may be determined according to productivity or device characteristics. The inorganic layer 31 may be formed by using a method such as chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD), sputtering, atomic layer deposition (ALD), or thermal evaporation.

[0042] Bonding sites to be bonded to the intermediate layer 32 are formed on the surface of the inorganic layer 31. The bonding sites, for example, may be an oxygen atomic layer. For this purpose, the surface of the inorganic layer 31 may be treated with oxygen plasma or ozone plasma. An M-H bond on the surface of the inorganic layer 31 may be changed to an M-OH bond by such an oxygen or ozone plasma treatment, where M denotes silicon or metal elements of the inorganic layer 31, such as silicon, aluminum, titanium, tantalum, hafnium, zirconium, cerium, tin, or magnesium.

[0043] A preliminary intermediate layer (not shown) is formed on the surface-treated inorganic layer 31 by using an organic monomer having a polymerizable double bond, such as a vinyl group or a carbonyl group, and a photopolymerization initiator. For example, the preliminary intermediate layer (not shown) may be formed of methacrylate, acrylate, or epoxy. Examples of the photopolymerization initiator may be an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, and a triazine-based compound. However, the preliminary intermediate layer is not limited thereto in embodiments of the invention. The above materials may be used alone or by mixing two or more thereof.

[0044] The preliminary intermediate layer (not shown) may be formed by using a flash evaporation method, an inkjet process, a screen printing method, a spin coating method, or an initiated chemical vapor deposition (iCVD) method forming vapor phase radicals at high temperatures. The preliminary intermediate layer (not shown) may be formed to a thickness of a few nanometres (few tens of angstrom (Å)), but the thickness of the preliminary intermediate layer is not limited thereto in embodiments of the invention. The organic monomer of the preliminary intermediate layer (not shown) may be bonded to the bonding sites of the inorganic layer 31.

[0045] Next, a preliminary organic layer (not shown) may be formed on the preliminary intermediate layer (not shown). The preliminary organic layer (not shown), for example, may be formed of an acryl-based resin, a methacryl-based resin, an isoprene-based resin, a vinyl-based resin, an epoxy-based resin, a urethane-based resin, a cellulose-based resin, a perylene-based resin, an imide-based resin, or a mixture thereof. The preliminary organic layer (not shown), for example, may be formed by using a method such as a flash evaporation method, an inkjet process, a screen printing method, or a spin coating method.

[0046] Subsequently, the preliminary intermediate layer (not shown) and the preliminary organic layer (not shown) are cured by using ultraviolet (UV) or heat. A vinyl group of the organic monomer of the preliminary intermediate layer (not shown) is polymerized with an organic monomer of the preliminary organic layer (not shown), and the organic monomer of the preliminary organic layer (not shown) is polymerized with the organic monomer of the preliminary intermediate layer (not shown) and another monomer of an organic layer (not shown). After a curing process, the preliminary intermediate layer (not shown) becomes the intermediate layer 32 and the preliminary organic layer (not shown) becomes the organic layer 33. Thus, the intermediate layer 32 is bonded to the organic layer 33 according to such polymerizations and the organic layer 33 forms a resin layer or a polymer layer.

[0047] FIG. 2 is a diagram conceptually illustrating a process, in which an intermediate layer forms a bond between an inorganic layer and an organic layer, according to an embodiment of the present invention.

[0048] Referring to FIG. 2, in step S1, the inorganic layer having a -H bond on a surface of the inorganic layer is prepared.

[0049] Then in step S2, the -H bond on the surface of the inorganic layer is changed to a -OH bond by a surface treatment.

[0050] In step S3, a preliminary intermediate layer, in which a part R1 is bonded to O of the inorganic layer and a vinyl group faces a surface, is formed on the surface-treated inorganic layer by using R1=CH2, an organic monomer having a vinyl group.

[0051] Next, in step S4, a preliminary organic layer is formed by using an organic monomer R2; and then the organic monomer R2 and the vinyl group of the preliminary intermediate layer are polymerized by curing to form a bond.

[0052] The intermediate layer thus is bonded to the organic layer and the inorganic layer, and as a result, adhesion between the organic layer and the inorganic layer is improved. Therefore, occurrence of peeling-off due to thermal stress may be prevented. Meanwhile, the bonding sites on the surface of the inorganic layer are not limited to only -OH and the polymerizable group of the organic monomer of the preliminary intermediate layer is not limited to only a vinyl group.

[0053] Since an intermediate layer is bonded to an organic layer and an inorganic layer, adhesion between the organic layer and the inorganic layer are improved, and thus, occurrence of peeling-off due to thermal stress may be prevented.

[0054] As discussed, embodiments of the present invention provide an organic electroluminescent display device, comprising: a substrate; an organic light-emitting device formed over the substrate; and an encapsulation layer formed over the organic light-emitting device and the substrate, the encapsulation layer comprising an anorganic layer and a polymer organic layer stacked with an intermediate layer formed of an organic monomer between the inorganic layer and the polymer organic layer, wherein one surface of the intermediate layer is bonded to the inorganic layer and another surface of the intermediate layer is bonded to the polymer organic layer by polymerization, and the inorganic layer is the closest layer of the encapsulation layer to the substrate.

[0055] In some embodiments, there could be a single stack of the inorganic layer, intermediate later and the polymer organic layer. In other embodiments, there could be a plurality of stacks of the inorganic layer, intermediate later and the polymer organic layer.

[0056] While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the scope of the present invention as defined by the following claims.


Claims

1. An organic electroluminescent display device (100), comprising:

a substrate (10);

an organic light-emitting device (20) formed over the substrate (10); and

an encapsulation layer (30) formed over the organic light-emitting device (20) and the substrate (10), the encapsulation layer (30) comprising an inorganic layer (31) and a polymer organic layer (33) stacked with an intermediate layer (32) formed of an organic monomer between the inorganic layer (31) and the polymer organic layer (33),

wherein one surface of the intermediate layer (32) is bonded to the inorganic layer (31), another surface of the intermediate layer (32) is bonded to the polymer organic layer (33) by polymerization, and the inorganic layer (31) is the closest layer of the encapsulation layer (30) to the substrate (10).


 
2. The organic electroluminescent display device (100) of claim 1, wherein the organic monomer which forms the intermediate layer (32) comprises a polymerizable double bond.
 
3. The organic electroluminescent display device (100) of claim 1 or 2, wherein the organic monomer which forms the intermediate layer (32) comprises methacrylate, acrylate, or epoxy.
 
4. The organic electroluminescent display device (100) of any one of claims 1 to 3, wherein the polymer organic layer (33) comprises an acryl-based resin, a methacryl-based resin, an isoprene-based resin, a vinyl-based resin, an epoxy-based resin, a urethane-based resin, a cellulose-based resin, a perylene-based resin, an imide-based resin, or a mixture of two or more thereof; and/or
wherein the inorganic layer (31) comprises silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, aluminum nitride, aluminum oxynitride, titanium oxide, titanium nitride, tantalum oxide, tantalum nitride, hafnium oxide, hafnium nitride, zirconium oxide, zirconium nitride, cerium oxide, cerium nitride, tin oxide, or tin nitride.
 
5. The organic electroluminescent display device (100) of any one of claims 1 to 4, wherein the inorganic layer (31) is bonded to the intermediate layer (32) through bonding sites on a surface of the inorganic layer (31);
optionally wherein the bonding sites are derived from an -OH group.
 
6. The organic electroluminescent display device (100) of any one of claim 1 to 5, wherein the encapsulation layer (30) comprises a plurality of the inorganic layers (31), a plurality of the polymer organic layers (33) between the plurality of inorganic layers (31), and a plurality of the intermediate layers (32) between the inorganic layers (31) and the polymer organic layers (33).
 
7. The organic electroluminescent display device (100) of any one of claims 1 to 6, wherein the organic light-emitting device (20) comprises a first electrode (21), a second electrode (23), and an organic emissive layer (22) between the first electrode (21) and the second electrode (23).
 
8. The organic electroluminescent display device (100) of any one of claims 1 to 7, wherein the organic light-emitting device (20) further comprises at least one of a hole injection layer (HIL), a hole transport layer (HTL), an electron injection layer (EIL), and an electron transport layer (ETL) between the first electrode (21) and the second electrode (23).
 
9. A method of fabricating an organic electroluminescent display device (100), the method comprising:

providing a substrate (10);

forming an organic light-emitting device (20) over the substrate (10); and

forming an encapsulation layer (30) over the organic light-emitting device (20) and the substrate (10), the encapsulation layer (30) including an inorganic layer (31) and a polymer organic layer (33) stacked with an intermediate layer (32) formed of a first organic monomer between the inorganic layer (31) and the polymer organic layer (33),

wherein one surface of the intermediate layer (32) is bonded to the inorganic layer (31) through bonding sites on a surface of the inorganic layer (31), another surface of the intermediate layer (32) is bonded to the polymer organic layer (33) by polymerization, and the inorganic layer (31) is the closest layer of the encapsulation layer (30) to the substrate (10).


 
10. The method of claim 9, wherein the forming of the encapsulation layer (30) comprises:

forming the inorganic layer (31);

forming bonding sites on the surface of the inorganic layer (31);

forming a preliminary intermediate layer on the surface of the inorganic layer (31) by using the first organic monomer, the first organic monomer being bonded to the bonding sites formed on the surface of the inorganic layer (31);

forming a preliminary organic layer on the preliminary intermediate layer by using a second organic monomer; and

curing the first organic monomer and the second organic monomer to form the intermediate layer (32) and the polymer organic layer (33).


 
11. The method of claim 10, wherein the forming of the preliminary intermediate layer is performed by flash evaporation, inkjet processing, screen printing, or spin coating.
 
12. The method of claim 10, wherein formation of the preliminary intermediate layer is performed by initiated chemical vapor deposition (iCVD);
optionally wherein a photopolymerization initiator is used with the first organic monomer in the formation of the preliminary intermediate layer.
 
13. The method of any one of claims 9 to 12, wherein the first organic monomer comprises a polymerizable double bond and a part including the polymerizable double bond is positioned on the surface of the preliminary intermediate layer opposite to the inorganic layer (31); optionally wherein the part including the polymerizable double bond comprises a vinyl group or a carbonyl group.
 
14. The method of any one of claims 9 to 13, wherein the first organic monomer comprises methacrylate, acrylate, or epoxy.
 
15. The method of any one of claims 9 to 14, wherein the preliminary organic layer is formed by using a flash evaporation method, an inkjet process, a screen printing method, or a spin coating method; and/or
wherein the curing comprises thermal curing or ultraviolet (UV) curing.
 


Ansprüche

1. Organische elektrolumineszierende Anzeigevorrichtung (100), umfassend:

ein Substrat (10);

eine über dem Substrat (10) ausgebildete organische lichtemittierende Vorrichtung (20); und

eine über der organischen lichtemittierenden Vorrichtung (20) und dem Substrat (10) ausgebildete Verkapselungsschicht (30), wobei die Verkapselungsschicht (30) eine anorganische Schicht (31) und eine organische Polymerschicht (33) umfasst, die mit einer Zwischenschicht (32) gestapelt sind, die aus einem organischen Monomer zwischen der anorganischen Schicht (31) und der organischen Polymerschicht (33) gebildet ist, wobei eine Oberfläche der Zwischenschicht (32) an die anorganische Schicht (31) gebunden ist, eine weitere Oberfläche der Zwischenschicht (32) durch Polymerisation an die organische Polymerschicht (33) gebunden ist und die anorganische Schicht (31) die dem Substrat (10) am nächsten gelegene Schicht der Verkapselungsschicht (30) ist.


 
2. Organische elektrolumineszierende Anzeigevorrichtung (100) nach Anspruch 1, wobei das organische Monomer, das die Zwischenschicht (32) ausbildet, eine polymerisierbare Doppelbindung umfasst.
 
3. Organische elektrolumineszierende Anzeigevorrichtung (100) nach Anspruch 1 oder 2, wobei das organische Monomer, das die Zwischenschicht (32) ausbildet, Methacrylat, Acrylat oder Epoxid umfasst.
 
4. Organische elektrolumineszierende Anzeigevorrichtung (100) nach einem der Ansprüche 1 bis 3, wobei die organische Polymerschicht (33) ein Harz auf Acryl-Basis, ein Harz auf Methacryl-Basis, ein Harz auf Isopren-Basis, ein Harz auf Vinyl-Basis, ein Harz auf Epoxid-Basis, ein Harz auf Urethan-Basis, ein Harz auf Cellulose-Basis, ein Harz auf Perylen-Basis, ein Harz auf Imid-Basis oder eine Mischung aus zwei oder mehr davon umfasst; und/oder
wobei die anorganische Schicht (31) Siliciumoxid, Siliciumnitrid, Siliciumoxynitrid, Aluminiumoxid, Aluminiumnitrid, Aluminiumoxynitrid, Titanoxid, Titannitrid, Tantaloxid, Tantalnitrid, Hafniumoxid, Hafniumnitrid, Zirconiumoxid, Zirconiumnitrid, Ceroxid, Cernitrid, Zinnoxid oder Zinnnitrid umfasst.
 
5. Organische elektrolumineszierende Anzeigevorrichtung (100) nach einem der Ansprüche 1 bis 4, wobei die anorganische Schicht (31) über Bindungsstellen auf einer Oberfläche der anorganischen Schicht (31) an die Zwischenschicht (32) gebunden ist;
wobei die Bindungsstellen gegebenenfalls von einer -OH-Gruppe abgeleitet sind.
 
6. Organische elektrolumineszierende Anzeigevorrichtung (100) nach einem der Ansprüche 1 bis 5, wobei die Verkapselungsschicht (30) eine Mehrzahl der anorganischen Schichten (31), eine Mehrzahl der organischen Polymerschichten (33) zwischen der Mehrzahl von anorganischen Schichten (31) und eine Mehrzahl der Zwischenschichten (32) zwischen den anorganischen Schichten (31) und den organischen Polymerschichten (33) umfasst.
 
7. Organische elektrolumineszierende Anzeigevorrichtung (100) nach einem der Ansprüche 1 bis 6, wobei die organische lichtemittierende Vorrichtung (20) eine erste Elektrode (21), eine zweite Elektrode (23) und eine organische Emitterschicht (22) zwischen der ersten Elektrode (21) und der zweiten Elektrode (23) umfasst.
 
8. Organische elektrolumineszierende Anzeigevorrichtung (100) nach einem der Ansprüche 1 bis 7, wobei die organische lichtemittierende Vorrichtung (20) ferner mindestens eines von einer Lochinjektionsschicht (hole injection layer - HIL), einer Lochtransportschicht (hole transport layer - HTL), einer Elektroneninjektionsschicht (electron injection layer-EIL) und einer Elektronentransportschicht (electron transport layer - ETL) zwischen der ersten Elektrode (21) und der zweiten Elektrode (23) umfasst.
 
9. Verfahren zum Herstellen einer organischen elektrolumineszierenden Anzeigevorrichtung (100), wobei das Verfahren Folgendes umfasst:

Bereitstellen eines Substrats (10);

Ausbilden einer organischen lichtemittierenden Vorrichtung (20) über dem Substrat (10); und

Ausbilden einer Verkapselungsschicht (30) über der organischen lichtemittierenden Vorrichtung (20) und dem Substrat (10), wobei die Verkapselungsschicht (30) eine anorganische Schicht (31) und eine organische Polymerschicht (33) aufweist, die mit einer Zwischenschicht (32) gestapelt sind, die aus einem ersten organischen Monomer zwischen der anorganischen Schicht (31) und der organischen Polymerschicht (33) gebildet ist,

wobei eine Oberfläche der Zwischenschicht (32) über Bindungsstellen auf einer Oberfläche der anorganischen Schicht (31) an die anorganische Schicht (31) gebunden ist, eine weitere Oberfläche der Zwischenschicht (32) durch Polymerisation an die organische Polymerschicht (33) gebunden ist und die anorganische Schicht (31) die dem Substrat (10) am nächsten gelegene Schicht der Verkapselungsschicht (30) ist.


 
10. Verfahren nach Anspruch 9, wobei das Ausbilden der Verkapselungsschicht (30) Folgendes umfasst:

Ausbilden der anorganischen Schicht (31);

Ausbilden von Bindungsstellen auf der Oberfläche der anorganischen Schicht (31);

Ausbilden einer vorläufigen Zwischenschicht auf der Oberfläche der anorganischen Schicht (31) unter Verwendung des ersten organischen Monomers, wobei das erste organische Monomer an die Bindungsstellen gebunden wird, die auf der Oberfläche der anorganischen Schicht (31) ausgebildet sind;

Ausbilden einer vorläufigen organischen Schicht auf der vorläufigen Zwischenschicht unter Verwendung eines zweiten organischen Monomers; und

Härten des ersten organischen Monomers und des zweiten organischen Monomers unter Bildung der Zwischenschicht (32) und der organischen Polymerschicht (33).


 
11. Verfahren nach Anspruch 10, wobei das Ausbilden der vorläufigen Zwischenschicht durch Entspannungsverdampfung, Tintenstrahlbearbeitung, Siebdruck oder Rotationsbeschichtung durchgeführt wird.
 
12. Verfahren nach Anspruch 10, wobei die Ausbildung der vorläufigen Zwischenschicht durch initiierte chemische Gasphasenabscheidung (initiated chemical vapor deposition-iCVD) durchgeführt wird;
wobei gegebenenfalls ein Photopolymerisationsinitiator mit dem ersten organischen Monomer bei der Ausbildung der vorläufigen Zwischenschicht verwendet wird.
 
13. Verfahren nach einem der Ansprüche 9 bis 12, wobei das erste organische Monomer eine polymerisierbare Doppelbindung umfasst und ein Teil, der die polymerisierbare Doppelbindung aufweist, auf der Oberfläche der vorläufigen Zwischenschicht gegenüber der anorganischen Schicht (31) angeordnet wird; wobei der Teil, der die polymerisierbare Doppelbindung aufweist, gegebenenfalls eine Vinylgruppe oder eine Carbonylgruppe umfasst.
 
14. Verfahren nach einem der Ansprüche 9 bis 13, wobei das erste organische Monomer Methacrylat, Acrylat oder Epoxid umfasst.
 
15. Verfahren nach einem der Ansprüche 9 bis 14, wobei die vorläufige organische Schicht unter Verwendung eines Entspannungsverdampfungsverfahrens, einer Tintenstrahlbearbeitung, eines Siebdruckverfahrens oder eines Rotationsbeschichtungsverfahrens ausgebildet wird; und/oder
wobei das Härten thermisches Härten oder Ultraviolett(UV)-Härten umfasst.
 


Revendications

1. Dispositif d'affichage électroluminescent organique (100) comprenant :

un substrat (10) ;

un dispositif luminescent organique (20) formé au-dessus du substrat (10) ; et

une couche d'encapsulation (30) formée au-dessus du dispositif luminescent organique (20) et du substrat (10), la couche d'encapsulation (30) comprenant une couche inorganique (31) et une couche organique polymère (33) empilées avec une couche intermédiaire (32) formée d'un monomère organique entre la couche inorganique (31) et la couche organique polymère (33),

dans lequel une surface de la couche intermédiaire (32) est collée à la couche inorganique (31), une autre surface de la couche intermédiaire (32) est collée à la couche organique polymère (33) par polymérisation, et la couche inorganique (31) est la couche de la couche d'encapsulation (30) la plus proche du substrat (10).


 
2. Dispositif d'affichage électroluminescent (100) selon la revendication 1, dans lequel le monomère organique qui forme la couche intermédiaire (32) comprend une double liaison polymérisable.
 
3. Dispositif d'affichage électroluminescent (100) selon la revendication 1 ou 2, dans lequel le monomère organique qui forme la couche intermédiaire (32) comprend un méthacrylate, un acrylate, ou un époxy.
 
4. Dispositif d'affichage électroluminescent (100) selon l'une quelconque des revendications 1 à 3, dans lequel la couche organique polymère (33) comprend une résine à base d'acrylate, une résine à base de méthacrylate, une résine à base d'isoprène, une résine à base de vinyle, une résine à base d'époxy, une résine à base d'uréthane, une résine à base de cellulose, une résine à base de pérylène, une résine à base d'imide, ou un mélange de deux ou plus de deux de celles-ci ; et/ou
dans lequel la couche inorganique (31) comprend de l'oxyde de silicium, du nitrure de silicium, de l'oxynitrure de silicium, de l'oxyde d'aluminium, du nitrure d'aluminium, de l'oxynitrure d'aluminium, de l'oxyde de titane, du nitrure de titane, de l'oxyde de tantale, du nitrure de tantale, de l'oxyde de hafnium, du nitrure de hafnium, de l'oxyde de zirconium, du nitrure de zirconium, de l'oxyde de cérium, du nitrure de cérium, de l'oxyde d'étain, ou du nitrure d'étain.
 
5. Dispositif d'affichage électroluminescent (100) selon l'une quelconque des revendications 1 à 4, dans lequel la couche inorganique (31) est collée à la couche intermédiaire (32) par l'intermédiaire de sites de collage sur une surface de la couche inorganique (31) ;
éventuellement dans lequel les sites de collage dérivent d'un groupe -OH.
 
6. Dispositif d'affichage électroluminescent (100) selon l'une quelconque des revendications 1 à 5, dans lequel la couche d'encapsulation (30) comprend une pluralité des couches inorganiques (31), une pluralité des couches organiques polymères (33) entre la pluralité de couches inorganiques (31), et une pluralité des couches intermédiaires (32) entre les couches inorganiques (31) et les couches organiques polymères (33).
 
7. Dispositif d'affichage électroluminescent (100) selon l'une quelconque des revendications 1 à 6, dans lequel le dispositif luminescent organique (20) comprend une première électrode (21), une deuxième électrode (23), et une couche émissive organique (22) entre la première électrode (21) et la deuxième électrode (23).
 
8. Dispositif d'affichage électroluminescent (100) selon l'une quelconque des revendications 1 à 7, dans lequel le dispositif luminescent organique (20) comprend en outre au moins l'une parmi une couche d'injection de trous (HIL), une couche de transport de trous (HTL), une couche d'injection d'électrons (EIL), et une couche de transport d'électrons (ETL) entre la première électrode (21) et la deuxième électrode (23).
 
9. Procédé de fabrication d'un dispositif d'affichage électroluminescent organique (100), le procédé comprenant les étapes consistant en :

l'obtention d'un substrat (10) ;

la formation d'un dispositif luminescent organique (20) au-dessus du substrat (10) ; et

la formation d'une couche d'encapsulation (30) au-dessus du dispositif luminescent organique (20) et du substrat (10), la couche d'encapsulation (30) comprenant une couche inorganique (31) et une couche organique polymère (33) empilées avec une couche intermédiaire (32) formée d'un monomère organique entre la couche inorganique (31) et la couche organique polymère (33),

dans lequel une surface de la couche intermédiaire (32) est collée à la couche inorganique (31) par l'intermédiaire de sites de collage sur une surface de la couche inorganique (31), une autre surface de la couche intermédiaire (32) est collée à la couche organique polymère (33) par polymérisation, et la couche inorganique (31) est la couche de la couche d'encapsulation (30) la plus proche du substrat (10).


 
10. Procédé selon la revendication 9, dans lequel la formation de la couche d'encapsulation (30) comprend :

la formation de la couche inorganique (31) ;

la formation de sites de collage sur la surface de la couche inorganique (31) ;

la formation d'une couche intermédiaire préliminaire sur la surface de la couche inorganique (31) par utilisation du premier monomère organique, le premier monomère organique étant collé aux sites de collage formés sur la surface de la couche inorganique (31) ;

la formation d'une couche organique préliminaire sur la couche intermédiaire préliminaire par utilisation d'un deuxième monomère organique ; et

le durcissement du premier monomère organique et du deuxième monomère organique pour former la couche intermédiaire (32) et la couche organique polymère (33).


 
11. Procédé selon la revendication 10, dans lequel la formation de la couche intermédiaire préliminaire est effectuée par évaporation éclair, traitement par jet d'encre, sérigraphie, ou revêtement centrifuge.
 
12. Procédé selon la revendication 10, dans lequel la formation de la couche intermédiaire préliminaire est effectuée par dépôt chimique en phase vapeur initié (iCVD) ;
éventuellement dans lequel un initiateur de polymérisation est utilisé avec le premier monomère organique dans la formation de la couche intermédiaire préliminaire.
 
13. Procédé selon l'une quelconque des revendications 9 à 12, dans lequel le premier monomère organique comprend une double liaison polymérisable et une partie contenant la double liaison polymérisable est positionnée sur la surface de la couche intermédiaire préliminaire opposée à la couche inorganique (31) ; éventuellement dans lequel la partie contenant la double liaison polymérisable comprend un groupe vinyle ou un groupe carbonyle.
 
14. Procédé selon l'une quelconque des revendications 9 à 13, dans lequel le premier monomère organique comprend un méthacrylate, un acrylate, ou un époxy.
 
15. Procédé selon l'une quelconque des revendications 9 à 14, dans lequel la couche organique préliminaire est formée par utilisation d'un procédé d'évaporation éclair, d'un traitement par jet d'encre, d'un procédé de sérigraphie, ou d'un procédé de revêtement centrifuge ; et/ou
dans lequel le durcissement comprend un durcissement thermique ou un durcissement aux ultraviolets (UV).
 




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Cited references

REFERENCES CITED IN THE DESCRIPTION



This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description