KR102321382B1 - polymer compound and organic light emitting display device having a thin film encapsulation comprising the same - Google Patents

Abstract

상기 식 중, R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, p, a, b 및 c 는 발명의 상세한 설명을 참조한다. Disclosed is a polymer compound in which the repeating unit is represented by the following Chemical Formula 1 according to one aspect.
<Formula 1>

In the above formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , p, a, b and c refer to the detailed description of the invention.

Description

BACKGROUND ART Polymer compound and organic light emitting display device having a thin film encapsulation comprising the same

The present invention 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 laminated, and a method for manufacturing the same.

The encapsulation technology of the organic light emitting device includes a substrate bonding technology of bonding an encapsulation substrate and a substrate including the organic light emitting device and a thin film encapsulation technology of forming an encapsulation film in a thin film form without an encapsulation substrate. Bonding of the encapsulation substrate and the substrate of the organic light emitting device uses an inorganic frit or an organic adhesive. For thin film encapsulation, an inorganic film such as _{AlO x} , SiN _x , SiO _x , or SiON may be used on the upper part of the panel.

Inorganic film for thin film encapsulation is thin but dense and has barrier properties against moisture and oxygen. However, the inorganic membrane is brittle and has weak mechanical properties due to stress. In particular, in the manufacturing process of the organic light emitting device, there are countless particles on the substrate. Since the inorganic layer on the particles is greatly affected by stress, the barrier properties of the inorganic layer are deteriorated.

Therefore, a structure was introduced to relieve the stress of the inorganic film while planarizing the irregular surface such as particles by introducing an organic film between the inorganic films. As the organic film, an acrylate-based material or an epoxy-based material is used.

In the case of acrylate-based materials, variously substituted carbonyl group derivatives are used in the acrylate backbone, and they are widely used because polymers can be easily made by radical polymerization. However, since the acrylate-based material is made of an aliphatic structure, the physical and chemical stability is low, and thus the structure may be easily decomposed.

In the case of epoxy-based materials, various aromatics are used by substituting an epoxy group. However, it is difficult to control the thickness because the structure is heavy and the deposition film formation efficiency is low, and it is difficult to control the polymerization rate because the reaction proceeds violently.

An object of the present invention is to provide an organic light emitting device having a thin film encapsulation structure that is easy to control film formation and is stable against physical and chemical influences applied during a process.

Disclosed is a polymer compound in which the repeating unit is represented by the following Chemical Formula 1 according to an aspect of the present invention.

<Formula 1>

In the above formula,

R ₁ is a linear, branched or cyclic C ₁ -C ₁₂ alkyl group,

R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, or a linear or branched C ₁ -C ₂₀ alkyl group,

R ₅ and R ₆ are each independently a hydrogen atom, or a linear or branched C ₁ -C ₆ alkyl group may be linked to each other to form a ring,

R ₇ is a hydrogen atom or a linear, branched or cyclic C ₁ -C ₁₂ alkyl group or C ₆ -C ₁₂ aryl group;

R ₈ is a hydrogen atom or a methyl group,

p is an integer from 0 to 12,

a, b and c are molar ratios, a+b+c=1, 0.5≤a≤0.9, 0.05≤b≤0.2, 0.05≤c≤0.3.

Two or more of the polymer compounds may include a cross-linking bond that shares any one or each of _{R 1} and R _{7 .}

Three or more of the high molecular compounds may include a cross-linking bond in which _{R 7 which is a branched alkyl group is shared.} In this case, two or more of the cross-linked polymer compounds may include an additional cross-linking bond in which _{R 1 is shared.}

A substrate according to another aspect of the present invention; an organic light emitting device on the substrate; and an encapsulation layer in which an inorganic layer and an organic layer are alternately stacked on the organic light emitting device, wherein the organic layer includes the polymer compound.

The thin film encapsulation structure including the polymer compound can provide an organic electroluminescent display device with improved film-forming properties control, stability against physical and chemical influences applied during the process, and improved protection against moisture and external air.

1 is a cross-sectional view schematically illustrating an organic light emitting display device according to an embodiment of the present invention.
2 is an optical micrograph of a surface of an organic electroluminescent display of a comparative example after 240 hours of driving.
3 is an optical micrograph of the surface of the organic electroluminescence display according to the embodiment after 240 hours of driving.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided so that the disclosed content may be thorough and complete, and that the spirit of the present invention may be sufficiently conveyed to those skilled in the art. In the drawings, the thicknesses of layers and regions are exaggerated for clarity. Like reference numerals refer to like elements throughout.

According to an embodiment, a polymer compound in which the repeating unit is represented by the following Chemical Formula 1 is disclosed.

<Formula 1>

The repeating unit of Formula 1 includes a moiety A1, a moiety B1, and a moiety C1, so that a hybrid polymer of norbornene and acrylate may be formed.

In Formula 1,

R ₁ is a linear, branched or cyclic C ₁ -C ₁₂ alkyl group. R ₂ , R ₃ and R ₄ are each independently a hydrogen atom or a linear or branched C ₁ -C ₂₀ alkyl group. R ₅ and R ₆ may be each independently a hydrogen atom or a linear or branched C ₁ -C ₆ alkyl group and may be connected to each other to form a ring. R ₇ is a hydrogen atom or a linear, branched or cyclic C ₁ -C ₁₂ alkyl group or C ₆ -C ₁₂ aryl group. R ₈ is a hydrogen atom or a methyl group.

p is an integer from 0 to 12;

a, b, and c are molar ratios, and a+b+c=1, and may be 0.5≤a≤0.9, 0.05≤b≤0.2, and 0.05≤c≤0.3.

R ₁ is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a methyl-propyl group, a methyl-butyl group , dimethyl-propyl group, dimethyl-butyl group, methyl-pentyl group, dimethyl-pentyl group, trimethyl-butyl group, methyl-hexyl group, tetramethyl-butyl group, dimethyl-hexyl group, ethyl-hexyl group, methyl-hep Tyl group, trimethyl-pentyl group, trimethyl-hexyl group, ethylmethyl-hexyl group, dimethyl-heptyl group, ethyl-heptyl group, ethyldimethyl-hexyl group, tetramethyl-hexyl group, diethylmethyl-pentyl group, ethyltrimethyl- pentyl group, dimethyl-octyl group, trimethyl-heptyl group, ethyl-octyl group, trimethyl-octyl group, ethylmethyl-octyl group, methyl-decyl group, propyl-octyl group, propyl-nonyl group, isopropyl-nonyl group, ethyl-decyl group, methyl-undecyl group, dimethyl-decyl group, dimethyl-propyl-heptyl group, tetramethyl-octyl group, cyclopropane, cyclobutane, cyclopentane, cyclohexane, or norbornene.

R ₂ , R ₃ and R ₄ are, for example, independently of each other a hydrogen atom, or a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, methyl-propyl group, methyl-butyl group, dimethyl-propyl group , an ethyl-propyl group, a dimethyl-butyl group, an ethyl-butyl group, or a methyl-pentyl group.

R ₅ and R ₆ are each independently a hydrogen atom, or a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a methyl-propyl group, a methyl-butyl group , dimethyl-propyl group, dimethyl-butyl group, methyl-pentyl group, dimethyl-pentyl group, trimethyl-butyl group, methyl-hexyl group, tetramethyl-butyl group, dimethyl-hexyl group, ethyl-hexyl group, methyl-hep Tyl group, trimethyl-pentyl group, trimethyl-hexyl group, ethylmethyl-hexyl group, dimethyl-heptyl group, ethyl-heptyl group, ethyldimethyl-hexyl group, tetramethyl-hexyl group, diethylmethyl-pentyl group, ethyltrimethyl- It may include a pentyl group, a dimethyl-octyl group, a trimethyl-heptyl group, or an ethyl-octyl group.

R ₇ is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a methyl-propyl group, a methyl-butyl group , dimethyl-propyl group, dimethyl-butyl group, methyl-pentyl group, dimethyl-pentyl group, trimethyl-butyl group, methyl-hexyl group, tetramethyl-butyl group, dimethyl-hexyl group, ethyl-hexyl group, methyl-hep Tyl group, trimethyl-pentyl group, trimethyl-hexyl group, ethylmethyl-hexyl group, dimethyl-heptyl group, ethyl-heptyl group, ethyldimethyl-hexyl group, tetramethyl-hexyl group, diethylmethyl-pentyl group, ethyltrimethyl- pentyl group, dimethyl-octyl group, trimethyl-heptyl group, ethyl-octyl group, trimethyl-octyl group, ethylmethyl-octyl group, methyl-decyl group, propyl-octyl group, propyl-nonyl group, isopropyl-nonyl group, Ethyl-decyl group, methyl-undecyl group, dimethyl-decyl group, dimethyl-propyl-heptyl group, tetramethyl-octyl group, cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornene, phenyl group, naphthyl group, indene, or a biphenyl group; It may include a phenyl group substituted with a halogen group, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group, and the like, a naphthyl group, an indene group, a biphenyl group, and the like.

Meanwhile, two or more of the high molecular compounds may include a cross-linking bond that shares any one or each of _{R 1} and R _{7 .} For example, _{both ends of R 1} may be respectively bonded to carboxylate groups connected to norbornene of two polymers to form a crosslink between the two polymers. In addition, both ends of independently, or in addition to R ₁ R ₇ are each coupled to two carboxylate groups of the main chain of the polymer can form a cross-linked bond between the two polymers. For example, two polymers may share a dodecyl group through a carboxylate group connected to norbornene to form a crosslink. Also, for example, the two polymers may share a dodecyl group through a carboxylate group of the main chain to form a crosslink. Such crosslinking may occur between two polymers or may occur like a mesh between several polymers.

Alternatively, three or more of the high molecular compounds may include a cross-linking bond in which _{R 7 which is a branched alkyl group is shared.} For example, three polymers may be connected to the three ends of the 12-dodecyl-tetracosanyl group through the carboxylate group of the main chain to form a crosslink. Such crosslinking may occur between three polymers or may occur like a mesh between several polymers. Meanwhile, two or more polymer compounds cross-linked through _{R 7} may include an additional cross-linking bond in which _{R 1 is shared.}

By including such a cross-linkage, the polymer becomes strong and the chemical resistance of the organic layer may be increased.

The weight average molecular weight of the polymer compound may be 1,000 to 100,000.

Since the polymer compound having the repeating unit of Formula 1 has an aliphatic cyclic polymer structure, it has higher physical/chemical stability to plasma or chemicals during processing than the aliphatic polymer.

Specifically, the repeating unit of the polymer compound may be represented by the following formula (2).

<Formula 2>

said R ₁ and R ₇ is R _{1 in Formula 1} and R ₇ Please refer to the description in relation to .

Two or more of the polymer compounds having a repeating unit represented by Formula 2 may include a cross-linking bond that shares one or each of _{R 1} and R _{7 as described above.} In addition, three or more of the polymer compounds having the repeating unit of Formula 2 may include a cross-linking bond that shares _{R 7 , which is a branched alkyl group, as described above.} In this case, two or more polymer compounds cross-linked through _{R 7} may include an additional cross-linking bond in which _{R 1 is shared.}

The polymer compound having a repeating unit represented by Formula 2 may have a weight average molecular weight of 1,000 to 100,000.

For example, the polymer compound may have a repeating unit represented by Formula 3 below.

<Formula 3>

The repeating unit of Formula 3 includes a moiety A13, a moiety B13, and a moiety C13, and thus may form a hybrid polymer of norbornene and acrylate.

In Formula 3, a plurality of l's are each independently an integer of 0 to 11.

Or, for example, the polymer compound may have a repeating unit represented by the following formula (4).

<Formula 4>

The repeating unit of Formula 4 includes an A2 moiety, a B2 moiety, and a C2 moiety, so that a hybrid polymer of norbornene and acrylate may be formed. In addition, the presence of cross-linking between the A2 moiety and the C2 moiety increases the density of the polymer and makes it stronger, so that the chemical resistance of the organic layer may be increased.

In Formula 4, a plurality of m is independently an integer of 1 to 12, a plurality of a may each independently have a different value, a plurality of b may each independently have a different value, and a plurality of c may each independently have different values.

Or, for example, the polymer compound may have a part or all of the repeating unit represented by the following formula (5).

<Formula 5>

The repeating unit of Formula 5 includes an A3 moiety, a B3 moiety, and a C3 moiety, thereby forming a hybrid polymer of norbornene and acrylate. In addition, the presence of cross-links between the A3 moiety and the C3 moiety increases the density of the polymer and makes it stronger, so that the chemical resistance of the organic layer may be increased.

In Formula 5, a plurality of n is independently an integer of 1 to 12, a plurality of a may have different values independently of each other, a plurality of b may have different values independently of each other, and a plurality of c may be They may have different values independently of each other.

In Formulas 3 to 5, a, b, and c are as described in relation to Formula 1, and a plurality of a, b, and c may have values independent of each other.

The organic layer 122 may be formed of a polymer compound represented by Chemical Formula 1 above. The organic layer 122 may relieve the stress of the inorganic layer 121 and serve as planarization. An optimum thickness of the organic layer 122 may be determined according to characteristics, productivity, and device characteristics of the inorganic layer 121 . For example, the organic layer 122 may have a thickness of 1 μm to 10 μm.

In the encapsulation layer 120 , the organic layer 122 and the inorganic layer 121 may be repeatedly stacked. In this case, the lowermost layer of the encapsulation layer 120 , that is, the uppermost layer of the encapsulation layer 120 and that is in contact with the organic light emitting device 110 , that is, the outermost layer of the encapsulation layer 120 may be the inorganic layer 121 . .

Hereinafter, a method of manufacturing an organic light emitting display device according to an embodiment of the present invention will be described.

First, a substrate 101 is provided. The substrate 101 may use a substrate made of various materials, such as a glass substrate, a plastic substrate, silicon, or metal. A buffer layer (not shown) is formed on the upper surface of the substrate 101 to prevent diffusion of impurity elements or ions from the substrate 101 into the upper thin film transistor or organic light emitting device 110 and penetration of moisture, etc., and to planarize the surface. can do. In addition, a thin film transistor (not shown) is formed on the substrate 101 as a circuit for driving the organic light emitting device 110 .

An organic light emitting diode 110 electrically connected to the thin film transistor (not shown) is formed on the substrate 101 . The organic light emitting diode 110 includes a first electrode 111 , a second electrode 115 , and an organic light emitting layer 113 therebetween.

The first electrode 111 may be an anode electrode, and in this case, the first electrode 111 may be formed by selecting a material having a high work function to facilitate hole injection. The first electrode 111 may be a transmissive electrode or a reflective electrode. The first electrode 111 is, for example, ITO (indium tin oxide), IZO (indium zinc oxide), ZnO (zinc oxide), AZO (Al doped zinc oxide), In ₂ O ₃ (indium oxide) or SnO ₂ (tin oxide) can be formed. Alternatively, the first electrode 111 may include magnesium (Mg), silver (Ag), aluminum (Al), aluminum: lithium (Al: Li), calcium (Ca), silver: indium tin oxide (Ag: ITO), magnesium: The reflective electrode may be formed using indium (Mg:In) or magnesium:silver (Mg:Ag). The first electrode 111 may be formed in a single layer or a multilayer structure of two or more. The first electrode 111 may be formed through a deposition method or a sputtering method.

The organic light emitting layer 113 includes at least an emissive layer (EML), in addition to a hole injection layer (HIL), a hole transport layer (HTL), and an electron transport layer (ETL). ), an electron transport layer (EIL: Electron Injection Layer), and the like may be further included. The organic light emitting layer 113 may be formed of a low-molecular or high-molecular material, and may be formed using various methods such as a vacuum deposition method, a spin coating method, a casting method, a LB method, and the like.

The hole injection layer (HIL) is a phthalocyanine compound such as copper phthalocyanine, DNTPD (N,N'-diphenyl-N,N'-bis-[4-(phenyl-m-tolyl-amino)-phenyl]-biphenyl-4 ,4'-diamine, N,N'-diphenyl-N,N'-bis-[4-(phenyl-m-tolyl-amino)-phenyl]-biphenyl-4,4'-diamine), m- MTDATA(4,4',4"-tris(3-methylphenylphenylamino)triphenylamine, 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine), TDATA(4,4'4"-Tris( N,N-diphenylamino)triphenylamine, 4,4',4"-tris(N,N'-diphenylamino)triphenylamine), 2T-NATA(4,4',4"-tris{N-(2) -naphthyl)-N-phenylamino}-triphenylamine, 4,4',4"-tris{N,-(2-naphthyl)-N-phenylamino}-triphenylamine), PEDOT/PSS (Poly(3, 4-ethylenedioxythiophene)/Poly(4-styrenesulfonate), poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate)), Pani/DBSA(Polyaniline/Dodecylbenzenesulfonic acid, polyaniline/dodecylbenzenesulfonic acid) , Pani/CSA (Polyaniline/Camphor sulfonicacid, polyaniline/camphorsulfonic acid) or PANI/PSS (Polyaniline)/Poly(4-styrenesulfonate) or polyaniline/poly(4-styrenesulfonate)) doesn't happen

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

The electron transport layer is Alq ₃ , BCP (2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-Diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline), TAZ(3-(4-Biphenylyl)-4-phenyl-5-tert-butylphenyl-1 ,2,4-triazole, 3-(4-biphenylyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole), NTAZ(4-(Naphthalen-1-yl)- 3,5-diphenyl-4H-1,2,4-triazole, 4- (naphthalen-1-yl) -3,5-diphenyl-4H-1,2,4-triazole), tBu-PBD (2 -(4-Biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole, 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3, 4-oxadiazole), BAlq(Bis(2-methyl-8-quinolinolato-N1,O8)-(1,1'-Biphenyl-4-olato)aluminum, bis(2-methyl-8-quinolinolato) -N1,O8)-(1,1'-biphenyl-4-orato)aluminum), Bebq ₂ (beryllium bis(benzoquinolin-10-olate, beryllium bis(benzoquinolin-10-noate)), ADN (9,10-di(naphthalene-2-yl)anthrascene, 9,10-di(naphthalene-2-yl)anthrascene), etc., but is not limited thereto.

The electron injection layer EIL may be formed using a material such as LiF, NaCl, CsF, Li2O, BaO, or Liq.

The emission layer EML may be formed to include a host material and a dopant material.

As a host, for example, Alq ₃ (tris(8-quinolinolate)aluminum), CBP(4,4'-bis(N-carbazolyl)-1,1'-biphenyl, 4,4'-bis(N) -carbazolyl)-1,1'-biphenyl), PVK(poly(n-vinylcabazole), poly(N-vinylcarbazole)), ADN(9,10-di(naphthalene-2-yl)anthracene, 9 ,10-di(naphthalen-2-yl)anthracene), TCTA(4,4',4''-Tris(carbazol-9-yl)-triphenylamine, 4,4',4''-tris(carbazole- 9-yl)-triphenylamine), TPBI (1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene, 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene ), TBADN (3-tert-butyl-9,10-di(naphth-2-yl) anthracene, 3-tert-butyl-9,10-di(naphth-2-yl) anthracene), DSA (distyrylarylene, distyrylarylene), E3 or CDBP (4,4'-bis(9-carbazolyl)-2,2'-dimethyl-biphenyl, 4,4'-bis(9-carbazolyl)-2,2'-dimethyl -biphenyl) and the like may be used, but the present invention is not limited thereto.

As dopants, PtOEP (Pt(II) octaethylporphine: Pt(II) octaethylporphine), Ir(piq) ₃ (tris(2-phenylisoquinoline)iridium: tris(2-phenylisoquinoline)iridium), Btp ₂ Ir ( acac) (bis(2-(2'-benzothienyl)-pyridinato-N,C3')iridium(acetylacetonate): bis(2-(2'-benzothienyl)-pyridinato-N,C3')iridium ( Acetylacetonate)), Ir(ppy) ₃ (tris(2-phenylpyridine) iridium: tris(2-phenylpyridine) iridium), Ir(ppy) ₂ (acac) (Bis(2-phenylpyridine)(Acetylacetonato)iridium( III): Bis (2-phenylpyridine) (acetylaceto) iridium (III)), Ir (mppy) ₃ (tris (2- (4-tolyl) phenylpiridine) iridium: tris (2- (4-tolyl) phenylpyridine ) iridium), C545T (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: 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), F ₂ Irpic (Bis[3,5-difluoro-2-(2-pyridyl)phenyl](picolinato)iridium( III): bis[3,5-difluoro-2-(2-pyridyl)phenyl (picolinato) iridium (III)), (F ₂ ppy) ₂ Ir(tmd), Ir(dfppz) ₃ , DPVBi (4,4'-bis(2,2'-diphenylethen-1-yl)biphenyl: 4,4'-bis(2,2'-diphenylethen-1-yl)biphenyl), DPAVBi (4 ,4'-Bis[4-(diphenylamino)styryl]biphenyl: 4,4'-bis(4-diphenylaminostyryl) Lil) biphenyl), TBPe (2,5,8,11-tetra-tert-butyl perylene: 2,5,8,11-tetra-tert-butyl perylene), etc. may be used, but the present invention is not limited thereto. .

The second electrode 115 may be a cathode electrode, and in this case, the second electrode 115 may be formed using a metal having a low work function, an alloy, an electrically conductive compound, and a mixture of two or more thereof. The second electrode 115 may be formed of, for example, a transparent electrode or a reflective electrode. When the second electrode 115 is a transparent electrode, lithium (Li), calcium (Ca), aluminum (Al), magnesium (Mg), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), LiF It can be formed as a thin film formed of -Al, LiF-Ca or a compound thereof and an auxiliary electrode formed of a transparent conductive material such as _{ITO, IZO, ZnO or In 2} O _{3 thereon.} In contrast, when the second electrode 115 is a reflective electrode, for example, lithium (Li), calcium (Ca), aluminum (Al), magnesium (Mg), magnesium-indium (Mg-In), and magnesium - It can be formed of silver (Mg-Ag), LiF-Al, LiF-Ca, or a compound thereof. The second electrode 115 may be formed by sputtering or vacuum deposition.

An encapsulation layer 120 is formed on the organic light emitting device 110 .

The inorganic layer 121 is, for example, 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, It may be formed from at least one of zirconium nitride, cerium oxide, cerium nitride, tin oxide, tin nitride, and magnesium oxide. An optimal thickness of the inorganic layer 121 may be determined according to productivity or device characteristics. For example, the inorganic layer 121 may be formed to a thickness of 500 nm to 10 μm. The inorganic layer 121 may be formed by a method such as chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD), sputtering, atomic layer deposition (ALD), or thermal evaporation.

An organic layer 122 is formed on the inorganic layer 121 . The organic layer 122 may be formed of a polymer compound having repeating units of Chemical Formulas 1 to 5 above. The organic layer 122 made of a polymer compound having repeating units of Chemical Formulas 1 to 5 may be formed by, for example, a radical polymerization method by mixing the corresponding monomers, flash evaporation, and UV curing, but limited thereto. it's not going to be By flash evaporation and UV curing, a mixture of monomers can be applied onto a substrate and polymerized to form a polymer organic layer.

An optimum thickness of the organic layer 122 may be determined according to characteristics, productivity, and device characteristics of the inorganic layer 121 . For example, the organic layer 122 may be formed to a thickness of 1 μm to 10 μm.

Meanwhile, the polymer compound having the repeating unit of Formula 1 may be used for thin film encapsulation of other electronic devices as well as thin film encapsulation of organic light emitting devices. In addition, the polymer compound having the repeating unit of Formula 1 may be used for planarization of a metal layer of an electronic device, planarization of particles generated in a manufacturing process of an electronic device, and the like.

synthesis method

Synthesis of a polymer compound having a repeating unit of Formula 1

The polymer compound having the repeating unit of Formula 1 may be formed by radical polymerization of a monomer as shown in the following reaction scheme. Referring to the following reaction scheme, by irradiating UV to a mixture of monomer A1' corresponding to part A1 of Formula 1, monomer B1' corresponding to part B1, monomer C1' corresponding to part C1, and an initiator to form radicals, A polymer corresponding to Chemical Formula 1 may be synthesized by causing radicals to chain radical polymerization reaction. In this case, the molar ratio of A1', B1' and C1' may be adjusted according to the ratio of a, b, and c in Formula 1. As the initiator, an initiator suitable for the radical polymerization reaction may be used.

<Scheme 1>

_{R 1} in the above scheme and R ₇ is R _{1 in Formula 1} and R ₇ Please refer to the description in relation to .

Synthesis of a polymer compound having a repeating unit of Formula 3

Monomer A13' corresponding to A13 of Formula 3 may be synthesized according to Scheme 2 below.

<Scheme 2>

Monomer C13' corresponding to C13 of Formula 3 may be synthesized by the following Reaction Scheme 3.

<Scheme 3>

The polymer compound having a repeating unit of Formula 3 uses A13' and C13' instead of A1' and C1' in Scheme 1, and uses B1' in which _{R 5} and R _{6 are hydrogen, except that} It can be synthesized using the same method as the method for synthesizing a polymer compound having a repeating unit. In Schemes 2 and 3, when R ₁ is -(CH ₂ ) ₁ -CH ₃ , A13′ and C13′ correspond to A13 and C13 of Formula 3; In this case, the molar ratio of A13', B1' and C13' may be adjusted according to the ratio of a, b, and c in Formula 3.

Synthesis of a polymer compound having a repeating unit of Formula 4

Monomer A2' corresponding to A2 of Formula 4 may be synthesized according to Scheme 4 below.

<Scheme 4>

Monomer C2' corresponding to C2 of Formula 4 may be synthesized according to Scheme 5 below.

<Scheme 5>

The polymer compound having a repeating unit of Formula 4 uses A2′ and C2′ instead of A1′ and C1′ in Scheme 1, and _{B1′ in which R 5} and R ₆ are hydrogen is used, except that B1′ is repeated. It can be synthesized using the same method as the method for synthesizing a polymer compound having units. In this case, the molar ratio of A2', B1', and C2' may be adjusted according to the ratio of a, b, and c in Formula 4.

In Schemes 4 and 5, m is an integer from 1 to 12.

Synthesis of a polymer compound having a repeating unit of Formula 5

Monomer C3' corresponding to C3 of Formula 5 may be synthesized according to Scheme 6 below.

<Scheme 6>

The polymer compound having the repeating unit of Chemical Formula 5 is a repeating formula of Chemical Formula 1, except that A2' and C3' are used instead of A1' and C1' in Scheme 1, and _{B1' in which R 5} and R ₆ are hydrogen is used. A method for synthesizing a polymer compound having a unit can be synthesized using the same method. In this case, the molar ratio of A2', B1' and C3' may be adjusted according to the ratio of a, b, and c in Formula 5. In Scheme 5, n is an integer from 1 to 12.

Example

Corning's 15Ω/cm2 (1,200Å) ITO glass substrate was ultrasonically cleaned for 5 minutes using isopropyl alcohol and pure water, respectively, followed by UV ozone cleaning for 30 minutes to form an anode on the substrate. An organic light emitting device having a stacked structure including a hole transport layer, a light emitting layer, an electron transport layer, and a cathode was formed on the ITO glass substrate. An inorganic layer was formed by vacuum-depositing aluminum oxide at a thickness of 10,000 Å on the organic light emitting device. A mixture of monomer A2' (m=12), monomer C3' (n=12), monomer B1' (R ₅ and R ₆ are hydrogen) and an initiator on the inorganic layer was subjected to flash evaporation and UV curing method. to form an organic layer composed of a polymer compound (weight average molecular weight (Mw) of 7,000) including the repeating unit of Chemical Formula 5 by depositing at 20,000 Å. At this time, the molar ratio of monomer A2':monomer B1':monomer C3' in the mixture was 7:2:1.

Then, silicon nitride was again vacuum-deposited on the organic layer at a thickness of 10,000 Å to form an inorganic layer, thereby forming an organic electroluminescent display.

comparative example

An organic electroluminescent display device was formed in the same manner as in Example except that polyacrylate was used instead of the polymer compound of Example for the organic layer.

test

The occurrence of dark spots was observed every 48 hours while the organic electroluminescent display devices of Examples and Comparative Examples were driven at 85° C. and 90% humidity. 2 is an optical micrograph of the surface of the organic electroluminescent display of Example and Comparative Example after 240 hours of driving. As shown in the photo of FIG. 2 , in the organic electroluminescent display of the comparative example, a number of dark spots were generated after 240 hours. However, as shown in the photo of FIG. 3 , dark spots did not occur in the organic light emitting diode display according to the embodiment even after 240 hours had elapsed.

The acrylate used as the conventional organic layer may be damaged by plasma during the formation process of the inorganic layer. For example, thermal decomposition occurs as shown in the following reaction formula, and progressive dark spots may occur over time by the generated gas.

However, in the polymer compound having the repeating unit of Formula 5, thermal decomposition during the process is suppressed by the cyclic structure and cross-linking of norbornene, thereby preventing the occurrence of advanced dark spots.

101: substrate 110: organic light emitting device
111: first electrode 113: organic light emitting layer
115: first electrode 120: encapsulation layer
121: inorganic layer 122: organic layer

Claims (20)

A polymer compound in which the repeating unit is represented by the following formula (1):
<Formula 1>

In the above formula,
R ₁ is a linear, branched or cyclic C ₁ -C ₁₂ alkyl group,
R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, or a linear or branched C ₁ -C ₆ alkyl group,
R ₅ and R ₆ are each independently a hydrogen atom, or a linear or branched C ₁ -C ₆ alkyl group,
R ₇ is a hydrogen atom or a linear, branched or cyclic C ₁ -C ₁₂ alkyl group or C ₆ -C ₁₂ aryl group;
R ₈ is a hydrogen atom or a methyl group,
a, b and c are molar ratios, a+b+c=1, 0.5≤a≤0.9, 0.05≤b≤0.2, 0.05≤c≤0.3. The method of claim 1,
A polymer compound comprising a cross-linking bond in which two or more of the polymer compounds _{share any one or each of R 1} and R _{7 .} The method of claim 1,
A polymer compound comprising a cross-linking bond in which three or more of the polymer compounds _{share the R 7 , which is a branched alkyl group.} 4. The method of claim 3,
A polymer compound comprising an additional cross-link in which at least two of the cross-linked polymer compounds _{share the R 1 .} The method of claim 1,
A polymer compound having a weight average molecular weight of 1,000 to 100,000. The method of claim 1,
A polymer compound in which the repeating unit is represented by the following formula (2):
<Formula 2>

In the above formula, R ₁ and R ₇ are independently of each other a linear or branched C ₁ -C ₁₂ alkyl group of a polymer compound. 7. The method of claim 6,
A polymer compound comprising a cross-linking bond in which two or more of the polymer compounds _{share any one or each of R 1} and R _{7 .} 7. The method of claim 6,
A polymer compound comprising a cross-linking bond in which three or more of the polymer compounds _{share the R 7 , which is a branched alkyl group.} 9. The method of claim 8,
A polymer compound comprising an additional cross-link in which at least two of the cross-linked polymer compounds _{share the R 1 .} 7. The method of claim 6,
A high molecular weight compound having a weight average molecular weight of 1,000 to 100,000. The method of claim 1,
A polymer compound in which the repeating unit is represented by the following formula (3):
<Formula 3>

In the above formula, a plurality of l's are each independently an integer of 1 to 9. 3. The method of claim 2,
A polymer compound in which the repeating unit is represented by the following formula (4):
<Formula 4>

In the above formula, a plurality of m are each independently an integer of 1 to 12. 5. The method of claim 4,
A polymer compound in which some or all of the repeating units are represented by the following formula (5):
<Formula 5>

In the above formula, a plurality of n are each independently an integer of 1 to 12. Board;
an organic light emitting device on the substrate; and
an encapsulation layer in which an inorganic layer and an organic layer are alternately stacked on the organic light emitting device,
The organic layer is an organic light emitting display device comprising the polymer compound of any one of claims 1 to 13. 15. The method of claim 14,
The lowermost layer and the uppermost layer of the encapsulation layer are inorganic layers. 15. The method of claim 14,
The inorganic layer has a thickness of 500 nm to 10 μm. 15. The method of claim 14,
The organic layer has a thickness of 1 μm to 10 μm. 15. The method of claim 14,
The inorganic layer is 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 and at least one of cerium nitride, tin oxide, tin nitride, and magnesium oxide. 15. The method of claim 14,
The organic light emitting device includes a first electrode, a second electrode, and an organic light emitting layer between the first electrode and the second electrode. The organic light emitting display device of claim 19 , wherein the organic light emitting device further comprises at least one of a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer between the first electrode and the second electrode.

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