TW201540734A - Polymer compound and organic light-emitting display device having thin-film encapsulation structure including the polymer compound - Google Patents

Abstract

A polymer compound has a repeating unit represented by Formula 1 and an organic light-emitting display device including the polymer com pound. wherein R1, R2, R3, R4, R5, R6, R7, R8, p, a, b, and c are the same as described in the detailed description section of the present specification.

Description

Polymer compound and organic light emitting display device having the same according to the film package structure of the polymer compound [Priority statement]

This application is filed on April 18, 2014, submitted by the Korean Intellectual Property Office and assigned serial number 10-2014-0046933 and submitted on April 14, 2015, and assigned serial number 10 as scheduled. -2015-0052632, the application of the application "Polymer compound and organic light-emitting display device having a thin film encapsulation structure containing the polymer compound ( POLYMER COMPOUND AND ORGANIC LIGHT-EMITTING DISPLAY DEVICE HAVING THIN-FILM ENCAPSULATION STRUCTURE INCLUDING THE POLYMER COMPOUND ), the entire contents of this application are hereby incorporated by reference in its entirety in its entirety in its entirety in its entirety in its entirety in its entirety

The present invention relates to a polymer compound and an organic light-emitting display device having a thin film encapsulation structure including the polymer compound, and in particular to an organic light-emitting display device having a thin film encapsulation structure including inorganic a layer and an organic layer comprising the polymer compound.

A packaging technology for an organic light-emitting display device includes a substrate bonding technology in which a package substrate is bonded to a substrate including an organic light-emitting display device, and a thin film packaging technology in which the package film is formed into a film form without using a package substrate . The bonding of the package substrate to the substrate comprising the organic light-emitting display device can be performed using an inorganic glass frit and an organic binder. The thin film encapsulation technique can use an inorganic film formed of, for example, AlO _x , SiN _x , SiO _x , or SiON on a panel.

The inorganic film used for the film encapsulation is thin and highly dense, and due to these characteristics, The inorganic film has barrier properties against moisture and oxygen. However, the inorganic film is brittle, and thus exhibits poor mechanical properties when stress is applied thereto. In particular, in the manufacturing process of an organic light-emitting display device, a large number of particles are placed on a substrate and when an inorganic film is placed on such particles, it is highly affected by stress. Therefore, the barrier properties of the inorganic film can be lowered.

In response, an organic film is introduced between the inorganic film and the particles to make the particles uneven The uniform surface is flattened and the stress applied to the inorganic film is lowered. Herein, the organic film may be formed of an acrylate-based or epoxy-based material.

In the case of acrylate-based materials, the acrylate backbone is in various ways Substitution with a carbonyl derivative and the polymer can be readily formed by free radical polymerization. Therefore, acrylate-based materials are widely used. However, since the acrylate-based material has an aliphatic structure, it has low physical and chemical stability, and thus its structure can be easily decomposed.

In the case of epoxy-based materials, each aromatic group is taken through an epoxy group. generation. However, the epoxy-based material has a bulky structure and low film formation efficiency. Therefore, when the epoxy-based material is formed into a film, it is difficult to control the thickness of the film. Moreover, during the reaction, the epoxy-based material reacts violently and it is difficult to control the polymerization rate.

One or more exemplary embodiments of the present invention may include a polymer compound and an organic light emitting display device having a thin film encapsulation structure containing the polymer compound, the thin film encapsulation structure having easy film formation control and/or when Physical and chemical stability is exhibited when stress is applied thereto during the process.

Other aspects will be set forth in part in the description which follows.

According to one or more exemplary embodiments of the present invention, a polymer compound having a repeating unit represented by Formula 1 may be provided:

Wherein R ₁ may be a linear, branched or cyclic C ₁ -C ₁₂ alkyl group, and R ₂ , R ₃ and R ₄ may each independently be a hydrogen atom or a linear or branched C ₁ -C ₆ alkane And R ₅ and R ₆ may each independently be a hydrogen atom or a linear or branched C ₁ -C ₂₀ alkyl group and may be bonded to each other to form a ring, and R ₇ may be a hydrogen atom or a straight chain, branched or cyclic a C ₁ -C ₁₂ alkyl group or a C ₆ -C ₁₂ aryl group, R ₈ may be a hydrogen atom or a methyl group, p may be an integer of 0 to 12, and a, b and c may be a molar ratio, and may be Satisfying the condition a+b+c=1, where 0.5 a 0.9,0.05 b 0.2, and 0.05 c 0.3.

According to the present invention, one or more examples of embodiments, such polymer compound of two or more thereof may be crosslinked to share R ₁ and R ₇ or in any one of each.

According to one or more exemplary embodiments of the present invention, three or more of the polymer compounds may be crosslinked to share R ₇ having a branched alkyl group. Here, among the crosslinked polymer compounds, two or more polymer compounds may be additionally crosslinked to share R ₁ .

According to one or more exemplary embodiments of the present invention, an organic light emitting display device The substrate may include a substrate; an organic light-emitting device on the substrate; and an encapsulation layer on the organic light-emitting device, the package layer comprising an inorganic layer and an organic layer alternately stacked, wherein the organic layer may be The polymer compound is included.

100‧‧‧Organic light-emitting display device

101‧‧‧Substrate

110‧‧‧Organic lighting device

111‧‧‧First electrode

113‧‧‧Organic emission layer

115‧‧‧second electrode

120‧‧‧Encapsulation layer

121‧‧‧Inorganic layer

122‧‧‧Organic layer

A more complete understanding of the present invention, together with the appended claims, 1 is a schematic cross-sectional view of an organic light emitting display device according to an embodiment of the present invention; and FIG. 2 is an optical microscopic image of an organic light emitting display device after 240 hours of driving according to a comparative example according to an embodiment of the present invention. And FIG. 3 is an optical microscopic image of an organic light-emitting display device after being driven for 240 hours according to an embodiment of the present invention.

Example embodiments will now be described more fully hereinafter with reference to the accompanying drawings; phase Rather, the embodiments are provided so that this disclosure will be thorough and complete, and the exemplary embodiments will be fully conveyed to those skilled in the art. In the drawings, the dimensions of layers and regions may be exaggerated for clarity. Throughout the specification, like reference numerals indicate like elements.

A polymer compound according to an embodiment of the present invention may comprise a repeating unit represented by Formula 1:

The repeating unit represented by Formula 1 may include an A1 moiety, a B1 moiety, and a C1 moiety, and since these components are included, a mixed polymer of norbornene and acrylate may be formed.

In the above formula 1, R ₁ may be a linear, branched or cyclic C ₁ -C ₁₂ alkyl group; and R ₂ , R ₃ and R ₄ may each independently be a hydrogen atom, or a straight chain or a branched C. ₁ -C ₆ alkyl; R ₅ and R ₆ may each independently be a hydrogen atom, or a linear or branched C ₁ -C ₂₀ alkyl group and may be bonded to each other to form a ring; R ₇ may be a hydrogen atom or a linear chain , branched or cyclic C ₁ -C ₁₂ alkyl or C ₆ -C ₁₂ aryl; and R ₈ may be a hydrogen atom or a methyl group; p may be an integer from 0 to 12; and a, b and c may Mohr ratio and can satisfy the condition a+b+c=1, of which 0.5 a 0.9,0.05 b 0.2, and 0.05 c 0.3.

In some embodiments, R ₁ can be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, A Base-propyl, methyl-butyl, dimethyl-propyl, dimethyl-butyl, methyl-pentyl, dimethyl-pentyl, trimethyl-butyl, methyl-hexyl, Tetramethyl-butyl, dimethyl-hexyl, ethyl-hexyl, methyl-heptyl, trimethyl-pentyl, trimethyl-hexyl, ethylmethyl-hexyl, dimethyl-heptyl , ethyl-heptyl, ethyl dimethyl-hexyl, tetramethyl-hexyl, diethylmethyl-pentyl, ethyltrimethyl-pentyl, dimethyl-octyl, trimethyl- Heptyl, ethyl-octyl, trimethyl-octyl, ethylmethyl-octyl, methyl-indenyl, propyl-octyl, propyl-indenyl, isopropyl-indenyl, B Base-fluorenyl, methyl-undecyl, dimethyl-indenyl, dimethyl-propyl-heptyl, tetramethyl-octyl, cyclopropyl, cyclobutyl, cyclopentyl, ring Hexyl, or norbornanyl.

In some embodiments, R ₂ , R ₃ and R ₄ may each independently be a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a methyl-propyl group, a methyl-butyl group, Dimethyl-propyl, ethyl-propyl, dimethyl-butyl, ethyl-butyl, or methyl-pentyl.

In some embodiments, R ₅ and R ₆ may each independently be a hydrogen atom, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, methyl- Propyl, methyl-butyl, dimethyl-propyl, dimethyl-butyl, methyl-pentyl, dimethyl-pentyl, trimethyl-butyl, methyl-hexyl, tetramethyl Base-butyl, dimethyl-hexyl, ethyl-hexyl, methyl-heptyl, trimethyl-pentyl, trimethyl-hexyl, ethylmethyl-hexyl, dimethyl-heptyl, B -heptyl, ethyl dimethyl-hexyl, tetramethyl-hexyl, diethylmethyl-pentyl, ethyltrimethyl-pentyl, dimethyl-octyl, trimethyl-heptyl Or ethyl-octyl.

In some embodiments, R ₇ can be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, A Base-propyl, methyl-butyl, dimethyl-propyl, dimethyl-butyl, methyl-pentyl, dimethyl-pentyl, trimethyl-butyl, methyl-hexyl, Tetramethyl-butyl, dimethyl-hexyl, ethyl-hexyl, methyl-heptyl, trimethyl-pentyl, trimethyl-hexyl, ethylmethyl-hexyl, dimethyl-heptyl , ethyl-heptyl, ethyl dimethyl-hexyl, tetramethyl-hexyl, diethylmethyl-pentyl, ethyltrimethyl-pentyl, dimethyl-octyl, trimethyl- Heptyl, ethyl-octyl, trimethyl-octyl, ethylmethyl-octyl, methyl-indenyl, propyl-octyl, propyl-indenyl, isopropyl-indenyl, B Base-fluorenyl, methyl-undecyl, dimethyl-indenyl, dimethyl-propyl-heptyl, tetramethyl-octyl, cyclopropyl, cyclobutyl, cyclopentyl, ring Hexyl, norbornene, phenyl, naphthyl, anthracenyl, or biphenyl; or phenyl, naphthyl, anthracenyl, or biphenyl, each via a halogen group, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, or the like.

In some embodiments, two or more of the polymeric compounds can be crosslinked to share either or each of R ₁ and R ₇ . For example, the two ends of R ₁ may each be linked to a carboxylate group that is attached to the norbornene of the two polymers to form a crosslink between the two polymers. In some embodiments, independently or additionally, the two ends of R ₁ , R ₇ may each be linked to a carboxylate group of the backbone of two polymers to form a crosslink between the two polymers . For example, two polymers can share a dodecyl group by means of a carboxylate group attached to norbornene to form a crosslink bond. In some embodiments, the two polymers share dodecyl groups via the carboxylate groups of their backbone to form crosslink bonds. The crosslinks may be present between two polymers or a plurality of polymers to create a network structure.

In some embodiments, three or more of the polymer compounds may be crosslinked to share R ₇ as a branched alkyl group. For example, three polymers can be attached to the three ends of 12-dodecyl-tetracosyl by means of a carboxylate group of their backbone to form a crosslink. The crosslinks may be present between three polymers or a plurality of polymers to create a network structure. In some embodiments, the polymer compound by means of self-crosslinking of R _7, the two or more polymer compounds may additionally be crosslinked, at a common R _1.

Due to the inclusion of crosslinks, the polymer can have a rigid structure and thus can be shaped An organic layer with increased chemical resistance.

In some embodiments, the weight average molecular weight of the polymer compound can range from about 1,000 to about 100,000.

Due to the inclusion of the aliphatic cyclic polymer structure, the polymer compound comprising the repeating unit represented by Formula 1 may have higher physical and chemical stability against plasma or chemical materials during the process than the aliphatic polymer.

In detail, the repeating unit of the polymer compound can be represented by the following formula 2:

R ₁ and R _{7 in} Formula 2 are the same as those described in Formula 1 in combination with R ₁ and R ₇ .

In some embodiments, two or more of the polymer compounds having a repeating unit represented by Formula 2 may be cross-linked to share either or each of R ₁ and R ₇ , as above Said.

In some embodiments, three or more of the polymer compounds having a repeating unit represented by Formula 2 may be cross-linked to share R ₇ having a branched alkyl group. In this regard, of the polymer compounds crosslinked by means of R ₇ , two or more polymer compounds may be additionally crosslinked to share R ₁ .

In some embodiments, a polymer compound having a repeating unit represented by Formula 2 The material may have a weight average molecular weight of from about 1,000 to about 100,000.

For example, the polymer compound can have a repeating unit represented by Formula 3:

The repeating unit of Formula 3 may have an A13 moiety, a B13 moiety, and a C13 moiety, and due to the inclusion of these components, a mixed polymer of norbornene and acrylate may be formed.

The plurality of I in Formula 3 may each independently be an integer from 1 to 9.

In some embodiments, the polymer compound can have a repeating unit represented by Formula 4: <Formula 4>

The repeating unit of Formula 4 may have an A2 moiety, a B2 moiety, and a C2 moiety, and thus may form a mixed polymer of norbornene and acrylate. Moreover, in the presence of the crosslinking bond in the A2 portion and the C2 portion, the density and rigidity of the polymer compound can be increased, and thus the chemical resistance of the organic layer formed by using the polymer compound can be increased.

The plurality of m in Formula 4 may each independently be an integer from 1 to 12, and the plurality of a may each independently have different values, the plurality of b may each independently have different values, and the plurality of cs may each independently have different values. value.

In some embodiments, the polymer compound may have, in whole or in part, a repeating unit represented by Formula 5: <Formula 5>

The repeating unit of Formula 5 may have an A3 moiety, a B3 moiety, and a C3 moiety, and due to the inclusion of these components, a mixed polymer of norbornene and acrylate may be formed.

In some embodiments, the density and rigidity of the polymer compound may increase in the presence of the crosslinks in the A3 moiety and the C3 moiety, and thus the chemical resistance of the organic layer formed by using the polymer compound may be increase.

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

a, b, and c in Formulae 3 to 5 may be the same as those described in Formula 1, and a plurality of a, b, and c may each independently have different values.

1 is a schematic cross-sectional view of an organic light emitting display device 100 in accordance with an embodiment of the present invention.

Referring to FIG. 1 , an organic light emitting device 110 can be formed on a substrate 101 , and an encapsulation layer 120 can be formed on the organic light emitting device 110 .

The organic light-emitting device 110 can include a first electrode 111 and a second electrode 115, and an organic emission layer 113 formed between the first electrode 111 and the second electrode 115.

In an encapsulation layer 120, the organic layer 122 and the inorganic layer 121 may be alternately stacked. In this regard, the lowermost layer of the encapsulation layer 120 (ie, one of the encapsulation layers 120 contacting a layer of the organic light-emitting device 110) and the uppermost layer of the encapsulation layer 120 (ie, the outermost layer of the encapsulation layer 120) are inorganic layers 121. .

An organic layer 122 may comprise a polymer compound represented by Formula 1. The organic layer 122 can alleviate a stress applied to an inorganic layer 121 and can planarize the inorganic layer 121. The thickness of the organic layer 122 can be determined according to the characteristics and productivity of the inorganic layer 121, and device characteristics. For example, the thickness of the organic layer 122 can range from about 1 micron to about 10 microns.

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

First, a substrate 101 is provided. The substrate 101 may be a glass substrate, a plastic substrate, or a substrate formed of various materials such as tantalum or metal.

A buffer layer (not shown) may be formed on the substrate 101. The buffer layer prevents impurity elements or ions from the substrate 101 from diffusing to the thin film transistor of the organic light-emitting device 110 disposed above the substrate 101 and prevents moisture from permeating. Moreover, the buffer layer can flatten the surface.

In some embodiments, a thin film transistor (not shown) may be formed on the substrate 101 as an electrical circuit for driving the organic light emitting device 110.

The organic light-emitting device 110 can be formed on the substrate 101. The organic light emitting device 110 can Electrically connected to the thin film transistor. The organic light-emitting device 110 can include a first electrode 111 and a second electrode 115, and an organic emission layer 113 formed between the first electrode 111 and the second electrode 115.

The first electrode 111 can be an anode, and in this case, a high work function can be used The first electrode 111 is formed by allowing the material of the hole to be smoothly provided. The first electrode 111 may be a transmissive electrode or a reflective electrode.

The first electrode 111 can be made of, for example, indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), Al-doped zinc oxide (AZO), It is formed by indium oxide (In ₂ O ₃ ) or tin oxide (SnO ₂ ).

In some embodiments, the first electrode 111 can be formed as a reflection by using the following Electrode: magnesium (Mg), silver (Ag), aluminum (Al), aluminum: lithium (Al: Li), calcium (Ca), silver: indium tin oxide (Ag: ITO), or magnesium: indium (Mg: In Or magnesium: silver (Mg: Ag).

The first electrode 111 may have a single layer structure or a multilayer structure. The first electrode 111 can be borrowed Formed by deposition or sputtering.

The organic emission layer 113 may include at least one emissive layer; EML), and additionally comprising a hole injection layer (HIL), a hole transport layer (HTL), an electron transport layer (ETL), and an electron injection layer (electron) At least one of the injection layer; EIL).

The organic emission layer 113 can be formed using a low molecular weight material or a polymer, and can be borrowed It is formed by using various methods such as a vacuum deposition method, a spin coating method, a casting method, or a Langmuir-Blodgett (LB) method.

The HIL can be formed by using, for example, the following materials: phthalocyanine compounds (phthalocyanine compound) such as copper phthalocyanine, N, N'-diphenyl-N, N'-bis-[4-(phenyl-inter -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-extended ethyldioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS), polyaniline/ten Dialkylbenzenesulfonic acid (Pani/DBSA), polyaniline/camphorsulfonic acid (Pani/CSA), or (polyaniline)/poly(4-styrenesulfonate) (PANI/PSS), but other materials may Instead used to form the HIL.

The HTL can be obtained by using a carbazole derivative (for example, N-phenylcarbazole and polyethylene) Ketrazole), N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4'-diamine (TPD), N , N'-bis(1-naphthyl)-N,N'-diphenylbenzidine (NPB), or a material based on triphenylamine (for example, 4,4',4"-tris(N-carbazolyl) Triphenylamine (TCTA) is formed, but other materials may alternatively be used to form the HTL.

The ETL can be formed by using: Alq ₃ , 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 4,7-diphenyl-1,10 -phenanthroline (Bphen), 3-(4-biphenyl)-4-phenyl-5-t-butylphenyl-1,2,4-triazole (TAZ), 4-(naphthalene-1 -yl)-3,5-diphenyl-4H-1,2,4-triazole (NTAZ), 2-(4-biphenyl)-5-(4-t-butylphenyl)-1 , 3,4-oxadiazole (tBu-PBD), bis(2-methyl-8-quinolinol-N1,O8)-(1,1'-biphenyl-4-alcoholate) aluminum (bis(2-methyl-8-quinolinolato-N1,O8)-(1,1'-biphenyl-4-olato)aluminum, BAlq), bis(benzoquinolin-10-alcoholate) oxime (Bebq ₂ , or 9,10-di(naphthalen-2-yl)anthracene (ADN), but other materials may alternatively be used to form the ETL.

The EIL can be used by using LiF, NaCl, CsF, Li2O, BaO, Liq, or And so on.

The EML can comprise a host material and a dopant material.

Examples of the host material may be tris(8-hydroxyquinoline)aluminum (Alq ₃ ), 4,4'-bis(N-carbazolyl)-1,1'-biphenyl (CBP), poly(N- Vinyl carbazole) (PVK), 9,10-di(naphthalen-2-yl)anthracene (ADN), 4,4',4"-tris(carbazol-9-yl)-triphenylamine (TCTA), 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI), 3-tert-butyl-9,10-di(naphthalen-2-yl)anthracene (TBADN), double Distrrylarylene (DSA), 9,9-diethyl-2-(9,9-diethyl-2-(9,9-diethyl-9H-indol-2-yl)-9H-indole -7-yl)-9H-indole (E3) and 4,4'-bis(9-carbazolyl)-2,2'-dimethyl-biphenyl (CDBP), but are not limited thereto.

Examples of the dopant material may be octaethylporphyrin Pt(II) (PtOEP), tris(2-phenylisoquinoline)indole (Ir(piq) ₃ ), bis(2-(2'-benzene) And thienyl)-pyridyl-N,C3') (etherether pyruvate) ruthenium (Btp ₂ Ir(acac)), tris(2-phenylpyridine) ruthenium (Ir(ppy) ₃ ), bis(2-benzene Pyridyl) (acetylpyruvate) ruthenium (III) (Ir(ppy) ₂ (acac)), tris(2-(4-methylphenyl)phenylpyridine) ruthenium (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](picolinic acid)ruthenium (III) (F ₂ Irpic), ( F ₂ ppy) ₂ Ir(tmd), Ir(dfppz) ₃ , 4,4'-bis(2,2'-stilbene-1-yl)biphenyl (DPVBi), 4,4'-double [4 -(diphenylamino)styryl]biphenyl (DPAVBi), and 2,5,8,11-tetra-tert-butylindole (TBPe), but is not limited thereto.

The second electrode 115 can be a cathode, and in this case, the second electrode 115 can be It is prepared using a metal, an alloy, a conductive compound, or a mixture of two or more of these, each of which has a low work function.

The second electrode 115 may be, for example, a transparent electrode or a reflective electrode.

When the second electrode 115 is a transparent electrode, the second electrode 115 may include lithium (Li), calcium (Ca), aluminum (Al), magnesium (Mg), magnesium-indium (Mg-In), magnesium-silver ( A film formed of Mg-Ag), LiF-Al, LiF-Ca, or a mixture thereof, and an auxiliary electrode formed thereon using a transparent conductive material such as ITO, IZO, ZnO, or In ₂ O ₃ .

In some embodiments, when the second electrode 115 is a reflective electrode, for example, The second electrode 115 can be made of lithium (Li), calcium (Ca), aluminum (Al), magnesium (Mg), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), LiF-Al, LiF-Ca, or a mixture thereof, is formed. The second electrode 115 can be formed by using sputtering or vacuum deposition.

The encapsulation layer 120 may be formed on the organic light emitting device 110.

The inorganic layer 121 can be formed by using, for example, the following: yttrium oxide, lanthanum nitride, Yttrium oxynitride, aluminum oxide, aluminum nitride, aluminum oxynitride, titanium oxide, titanium nitride, tantalum oxide, tantalum nitride, hafnium oxide, tantalum nitride, zirconium oxide, zirconium nitride, hafnium oxide, nitridation Antimony, tin oxide, tin nitride, or magnesium oxide.

The optimum thickness of the inorganic layer 121 can be considered in consideration of productivity or device characteristics. Decide. For example, the inorganic layer 121 can have a thickness of from about 500 nanometers to about 10 microns. The inorganic layer 121 can be formed by chemical vapor deposition (CVD), plasma assisted chemical vapor deposition (PECVD), sputtering, atomic layer deposition (ALD), or thermal evaporation.

The organic layer 122 may be formed on the inorganic layer 121. The organic layer 122 can be used by using A polymer compound having a repeating unit represented by one of Formulas 1 to 5 is formed. The organic layer 122 formed of the polymer compound having the repeating unit of Formulas 1 to 5 can be formed by, for example, mixing, flash evaporation, or UV curing-induced radical polymerization of the corresponding monomers. However, other methods may be used to form the organic layer 122. A mixture of monomers can be applied to the substrate and polymerized to form a polymeric organic layer by flash evaporation and UV curing.

The thickness of the organic layer 122 can be considered in consideration of the characteristics, productivity, and loading of the inorganic layer 121. It is decided in the case of setting characteristics. For example, the thickness of the organic layer 122 can range from about 1 micron to about 10 micro. Within the range of meters.

A polymer compound having a repeating unit represented by Formula 1 can also be used for a film seal Other electronic devices than the organic light-emitting device film are installed. In some embodiments, a polymer compound having a repeating unit represented by Formula 1 can be used to planarize a metal layer of an electronic device and particles generated during fabrication of the electronic device.

resolve resolution

Synthesis of polymer compounds having repeating units represented by formula 1

The polymer compound having the repeating unit of Formula 1 can be reacted by the following reaction scheme 1 The free radical polymerization of the monomers illustrated in the above is formed. Referring to the following reaction scheme 1, the ultraviolet (UV) line irradiation includes the monomer A1', the monomer B1', and the monomer C1' (corresponding to the A1 portion, the B1 portion, and the C1 portion in the formula 1, respectively) and the initiation. The mixture of the agents forms a radical, and the formed radical continuously causes radical polymerization to synthesize a polymer compound having a repeating unit represented by Formula 1. In this regard, the molar ratios of A1', B1', and C1' can be controlled by considering the ratio of a, b, and c in Formula 1. The initiator can be selected from the group of initiators suitable for the free radical polymerization.

In Reaction Scheme 1, R ₁ to R ₇ may be the same as those described in the combination of R ₁ and R ₇ in Formula 1.

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

The monomer A13' corresponding to A13 in Formula 3 can be synthesized according to Reaction Scheme 2:

The monomer C13' corresponding to C13 in Formula 3 can be synthesized according to Reaction Scheme 3:

The polymer compound having the repeating unit of Formula 3 is synthesized in the same manner as the polymer compound used for the synthesis of the repeating unit of Formula 1, except that A13' and C13' are used instead of A1' and C1', respectively, in the reaction. B1' in which each of R ₅ and R ₆ is hydrogen is used in Scheme 1. Regarding Reaction Scheme 2 and Reaction Scheme 3, when R ₁ is -(CH ₂ ) _l -CH ₃ , A13' and C13' correspond to A13 and C13 in Formula 3, respectively. In this regard, the molar ratios of A13', B1', and C13' are determined by the ratio of a, b, and c in the visual formula 3.

Synthesis of polymer compounds having repeating units represented by formula 4

The monomer A2' corresponding to A2 in Formula 4 can be synthesized according to Reaction Scheme 4:

The monomer C2' corresponding to C2 in Formula 4 can be synthesized according to Reaction Scheme 5:

The polymer compound having the repeating unit of Formula 4 is synthesized in the same manner as the polymer compound used for the synthesis of the repeating unit of Formula 1, except that A2' and C2' are used instead of A1' and C1', respectively, and in the reaction In Scheme 1, B1' in which each of R5 and R6 is hydrogen is used. In this regard, the molar ratios of A2', B1', and C2' are determined by the ratio of a, b, and c in the visual formula 4.

m in Reaction Scheme 4 and Reaction Scheme 5 may be an integer from 1 to 12.

Synthesis of polymer compounds having repeating units represented by formula 5

The monomer C3' corresponding to C3 in Formula 5 can be synthesized according to Reaction Scheme 6:

The polymer compound having the repeating unit of the formula 5 is synthesized in the same manner as the polymer compound for synthesizing the repeating unit having the formula 1, except that A2' and C3' are used instead of A1' and C1', respectively. B1' in which each of R ₅ and R ₆ is hydrogen is used in Scheme 1. In this regard, the molar ratios of A2', B1', and C3' are determined by the ratio of a, b, and c in the visual formula 5. n in Reaction Scheme 6 may be an integer from 1 to 12.

Instance

Ultrasonic treatment of 15 ohm/cm ² (1,200 Å) ITO glass substrate manufactured by Corning, Inc. using isopropyl alcohol and pure water for 5 minutes each And then by exposing to ultraviolet light and ozone for 30 minutes to form an anode on the substrate. An organic light-emitting device having a stacked structure including a hole transport layer, an emission layer, an electron transport layer, and a cathode is formed on the ITO glass substrate. Alumina was vacuum deposited on the organic light-emitting device to form an inorganic layer having a thickness of 10,000 angstroms. Of a monomer A2 '(m = 12), monomer C3' (n = 12), the monomer B1 '(R ₅ and R ₆ are each hydrogen), and a mixture of the initiator to the deposition by flash evaporation The inorganic layer was UV-cured to form an organic layer having a thickness of 20,000 Å and formed of a polymer compound having a repeating unit of Formula 5 (weight average molecular weight (Mw) of 7,000). In this regard, the molar ratio of monomer A2':monomer B1':monomer C3' in the mixture is 7:2:1.

A tantalum nitride is vacuum deposited on the organic layer to form a thickness of 10,000 angstroms An inorganic layer to form an organic light emitting display device.

Comparative example

The organic light-emitting display device was fabricated in the same manner as in the examples except that the organic layer was formed by using a polyacrylate instead of the polymer compound having the repeating unit of the formula 5.

test

An organic light emitting display device manufactured according to the example and the comparative example is The formation of dark spots was monitored at a temperature of 85 ° C in 90% humidity and every 48 hours. Fig. 2 and Fig. 3 are optical microscopic images of the organic light-emitting display device manufactured according to this example and the comparative example, respectively, after being driven for 240 hours. As shown in Fig. 2, after driving for 240 hours, a plurality of black spots appeared on the organic light-emitting display device manufactured according to the comparative example. However, as shown in Fig. 3, black spots did not appear on the organic light-emitting display device manufactured according to the example even after driving for 240 hours.

The acrylate used in the prior art organic layer may be during the formation of the inorganic layer Damaged by the plasma. For example, as illustrated in the following scheme, thermal decomposition can occur, generating a gas that causes progressive dark spots over time, as shown in FIG.

However, in the case of a polymer compound having a repeating unit of the formula 5, In the cyclic structure and/or crosslinks of the norbornene structure, thermal decomposition during the process can be suppressed, and thus the formation of progressive black spots can be prevented, as shown in Fig. 3.

The organic light emitting display device according to an embodiment of the present invention may have a thin film package The structure has easy-to-control film formation characteristics, resistance to physical and chemical influences applied thereto during the process, and improved barrier properties against moisture and external gases.

It should be understood that the example embodiments are to be considered in a Purpose to consider. Descriptions of features or aspects of the various exemplary embodiments are generally considered to be applicable to other similar features or aspects in other example embodiments.

Although one or more exemplary embodiments of the present invention have been described with reference to the drawings, It will be understood by those skilled in the art that the present invention may be modified in various forms and details without departing from the spirit and scope of the invention.

101‧‧‧Substrate

110‧‧‧Organic lighting device

111‧‧‧First electrode

113‧‧‧Organic emission layer

115‧‧‧second electrode

120‧‧‧Encapsulation layer

121‧‧‧Inorganic layer

122‧‧‧Organic layer

Claims (20)

A polymer compound having a repeating unit represented by Formula 1: Wherein in Formula 1, R ₁ is a linear, branched or cyclic C ₁ -C ₁₂ alkyl group, and R ₂ , R ₃ , and R ₄ are each independently a hydrogen atom or a straight chain or a branched C ₁ -C ₆ alkyl, R ₅ and R ₆ are each independently a hydrogen atom or a linear or branched C ₁ -C ₂₀ alkyl group, R ₇ is a hydrogen atom or a straight chain, branched or cyclic C ₁ - C ₁₂ alkyl or C ₆ -C ₁₂ aryl, R ₈ is a hydrogen atom or a methyl group, and p is an integer from 0 to 12, and each of a, b and c is a molar ratio, and satisfies the condition a+b +c=1, where 0.5 a 0.9,0.05 b 0.2, and 0.05 c 0.3. The polymer compound of claim 1, wherein two or more of the polymer compounds are crosslinked to share either or each of R ₁ and R ₇ . The polymer compound of claim 1, wherein three or more of the polymer compounds are crosslinked to share R ₇ having a branched alkyl group. The polymer compound of claim 3, wherein among the crosslinked polymer compounds, two or more polymer compounds are additionally crosslinked to share R ₁ . The polymer compound of claim 1, wherein the polymer compound has a weight average molecular weight of from about 1,000 to about 100,000. The polymer compound of claim 1, wherein the repeating unit is represented by Formula 2: Wherein R ₁ and R ₇ are each independently a linear or branched C ₁ -C ₁₂ alkyl group. The polymer compound of claim 6, wherein two or more of the polymer compounds are crosslinked to share either or each of R ₁ and R ₇ . The polymer compound of claim 6, wherein three or more of the polymer compounds are crosslinked to share R ₇ having a branched alkyl group. The polymer compound of claim 8, wherein from among the crosslinked polymer compounds, two or more polymer compounds are additionally crosslinked to share R ₁ . The polymer compound of claim 6, wherein The polymer compound has a weight average molecular weight of from about 1,000 to about 100,000. The polymer compound of claim 1, wherein the repeating unit is represented by Formula 3: Wherein the plurality of I lines are each independently an integer from 1 to 9. The polymer compound of claim 2, wherein the repeating unit is represented by Formula 4: Wherein, the plurality of m series are each independently an integer of 1 to 12. The polymer compound of claim 4, wherein the repeating unit is partially or wholly represented by Formula 5: Wherein the plurality of n series are each independently an integer from 1 to 12. An organic light emitting display device comprising: a substrate; an organic light emitting device on the substrate; and an encapsulation layer on the organic light emitting device, the package layer comprising an inorganic layer and an organic layer alternately stacked Wherein the organic layer comprises the polymer compound as claimed in claim 1. The organic light-emitting display device of claim 14, wherein the encapsulation layer comprises a lowermost layer and an uppermost layer, each of which is an inorganic layer. The organic light-emitting display device of claim 14, wherein the inorganic layer has a thickness of from about 500 nm to about 10 μm. The organic light-emitting display device of claim 14, wherein the organic layer has a thickness of from about 1 micron to about 10 microns. The organic light-emitting display device of claim 14, wherein the inorganic layer comprises at least one selected from the group consisting of cerium oxide, cerium nitride, cerium oxynitride, aluminum oxide, aluminum nitride, aluminum oxynitride, and titanium oxide. Titanium nitride, tantalum oxide, tantalum nitride, hafnium oxide, tantalum nitride, zirconium oxide, zirconium nitride, hafnium oxide, tantalum nitride, tin oxide, tin nitride, and magnesium oxide. The organic light-emitting display device of claim 14, wherein the organic light-emitting device comprises a first electrode, a second electrode, and an organic emission 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 layer selected from the group consisting of: a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer, wherein the at least one layer It is located between the first electrode and the second electrode.