KR20180002547A - Composition and compound for encapsulating organic light emitting diode and oencapsulated apparatus comprising the same - Google Patents

Abstract

The present invention provides an encapsulating composition for an organic light emitting device which blocks moisture and oxygen penetrated from the outside to improve the reliability of a device member, and an encapsulated device comprising the same. The encapsulating composition of the present invention may contain a photocurable monomer represented by chemical formula 1, and an initiator.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealing compound for an organic electroluminescent device, a composition thereof, and an encapsulated device comprising the same. BACKGROUND ART [0002]

The present invention relates to a sealing composition for an organic electroluminescent device and an encapsulated device comprising the same.

In an organic light emitting diode (OLED), electrons injected from a cathode and holes injected from an anode are combined in an emission layer of an organic light emitting portion to form an electron-hole pair And a self-emitting flat panel display device in a process of recombination thereof. The OLED has the advantages of high luminous efficiency in the three primary colors of light, red, green, blue and white, low driving voltage and power consumption, wide viewing angle, and high response speed of pixels, .

 In addition, OLED devices are capable of realizing ultra-thin and lightweight displays that can be manufactured to a thickness of 1 mm or less on substrates such as glass or plastic, and are being actively studied in the field of flexible displays. However, in the case of an OLED device, the light emitting material and the electrode material are oxidized by oxygen or moisture, thereby causing problems such as a dark spot and a pixel shrinkage, resulting in a decrease in lifetime and efficiency.

Encapsulation technology that blocks oxygen or moisture from entering the OLED device is one of key technologies that must be developed.

These encapsulation technologies can be largely divided into three ways: Can (glass encapsulation), TFE (thin film encapsulation) and Hybrid. Each method can be divided into three types: a cover plate with a metal barrier or gas barrier Method and a TFE method which can be called a face sealing method which implements a barrier property with organic or inorganic multilayer thin film on the upper layer of the device and a plastic barrier film as a cover plate, It can be explained by the hybrid method of positioning the adhesive layer. A sealing method is disclosed in Korean Patent Publication No. 2011-0071039.

Can (Glass encap) method widely used until now is a technology to seal the glass powder by melting with laser or sealing with UV adhesive by placing OLED element between two glasses composed of substrate and lid. However, it has a disadvantage in that the heat conduction characteristic is poor due to the inert gas in the device, the cost due to the glass processing is increased due to the large surface area, and it is difficult to apply it to the manufacture of the flexible OLED panel requiring flexibility.

In order to compensate for the disadvantages of such a glass sealing technique, an OLED element is formed by alternately laminating an inorganic layer such as Al ₂ O ₃ having a high barrier property to oxygen or moisture and a polymer organic layer as a thin film, Thin film encapsulation (TFE), which is a multilayer thin film encapsulation technology, has been actively studied. Also, a simple sealing adhesive film (hybrid) technique for laminating the front surface of an OLED element with a film having moisture barrier property is actively being developed.

Therefore, the sealing material of the organic light emitting device should be applicable to a flexible OLED device, and it should also be applicable to an adhesive layer positioned between the passivation layer and the cover plate of the organic light emitting device in the hybrid mode.

The TFE method, which is a multi-layered encapsulation method, is a Brix method by Vitex, which has a water vapor permeability suitable for organic light emitting devices when a thin film multilayer structure is implemented by applying 4 to 6 pairs of Al ₂ O ₃ and organic barrier layers as inorganic barrier layers U.S. Patent 7767498.

The inorganic barrier layer may be a metal oxide / nitride such as AlxOy, SiOx, SiNy, SiOxNy, etc., and the inorganic barrier layer may be formed by a sputtering deposition method sputtering deposition, plasma enhanced chemical vapor deposition (PECVD), or the like.

The organic barrier layer should have transparency suitable for display characteristics while maintaining the flatness of the organic barrier layer over the thickness loss and the surface uniformity for the particles having a high energy in the process for forming the inorganic barrier layer. Particularly, in the process of forming the inorganic barrier layer, the metal oxide / nitride particles having a high energy impinge on the organic barrier layer in the process using the plasma, wherein the organic barrier layer has a plasma resistance .

Therefore, the organic barrier layer must have both flexibility suitable for flexible OLEDs and resistivity to the plasma process. Plasma resistance to the organic barrier layer is determined by the Ohnishi parameter expressed in Equation 1 and the " Limits to etch resistance for 193 nm single " in " Dry etch resistance of organic materials, "Journal of the Electrochemical Society, vol. -layer resists, "Proceedings of SPIE, vol. 2724, 365 (1995), the correlation between ring parameters represented by Equation 2 has been studied.

[Formula 1]

_{Ohnishi parameter = N T / (N} C -N O)

Here, N _T is the total number of atoms in the molecule, N _C is the number of carbon atoms, and N _O is the number of oxygen atoms. The Ohnishi parameter indicates the basic tendency of polymer etching, and most polymers are known to follow the tendency . Since then, the researchers have made a number of modifications based on the Ohnishi model, for example by combining ring parameters and carbon and oxygen content to improve prediction accuracy. These variants are suitable for experimental data rather than mathematical, but the explanation of the physical meaning is lacking "Plasma etch properties of organic BARCs" Proc. of SPIE Vol. 6923, 69232G, (2008). Here, it is explained that the ring parameter is a limited model in the case of a polymer including an aromatic ring.

In this paper, the Ohnishi parameter and the etch rate study showed that the etch rate using the O ₂ , CF ₄ , N ₂ / H _2, and Ohnishi parameter values in the range of 2 ~ 7 The larger the value, the faster the etch rate. That is, a low Ohnishi parameter value can be interpreted to have a high plasma resistance under the condition of using the above gas.

[Formula 2]

Ring parameter = M.W. of only aromatic carbon / M.W. total

U.S. Patent No. 7767498 discloses that the barrier properties of moisture and oxygen are more advantageous as the number of pairs of the organic barrier layer and the inorganic barrier layer is larger. However, the barrier properties of the barrier layer due to the foreign material incorporation And a decrease in the yield along with the decrease is reported as disadvantage.

In recent studies, in order to overcome the yield deterioration while maintaining the barrier properties, research has been conducted in the direction of increasing the thickness of the organic / inorganic barrier layer and decreasing the number of layers in the thin film multilayer structure, As the number of processes is reduced, the number of process steps is reduced, and the manufacturing cost can be reduced by overcoming the deterioration of the characteristics and the yield reduction due to foreign matter incorporation.

Accordingly, the present invention provides an ultraviolet curable encapsulant composition capable of forming a thick film in conformity with a development direction of a display that is converted from a rigid display to a flexible OLED, and having flexibility and plasma resistance during film formation.

It is an object of the present invention to provide a sealing composition having plasma resistance and suitable for a vapor deposition process and an inkjet process.

Another object of the present invention is to provide a sealing composition capable of forming a thick film and having flexibility.

It is still another object of the present invention to provide a sealing composition capable of forming a barrier layer for encapsulation of a member for an environmentally sensitive device.

The sealing composition of the present invention may contain a photo-curable monomer represented by the following formula (1) and an initiator

The present invention uses a sealing composition having acrylate derivatives bonded at the meta- position of phenyl, thereby increasing the adhesion of the sealing composition to the inorganic barrier layer after curing, thereby blocking water and oxygen penetrating from the outside, There is an effect that the reliability of the application member can be improved.

1 is an exemplary view illustrating an organic electroluminescent device according to an embodiment of the present invention.
2 is a view schematically showing an example of the structure of an electronic device including an organic electroluminescent device.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

It should be noted that, in adding reference numerals to the constituent elements of the drawings, the same constituent elements are denoted by the same reference symbols as possible even if they are shown in different drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected," "coupled," or "connected."

As used in this specification and the appended claims, unless stated otherwise, the following terms have the following meanings:

The term " halo "or" halogen ", as used herein, unless otherwise indicated, is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I).

As used herein, the term "alkyl" or "alkyl group " refers to a straight or branched Alkyl " means a radical of a saturated aliphatic group, including alkyl, cycloalkyl-substituted alkyl groups.

The term "haloalkyl group" or "halogenalkyl group" as used in the present invention means an alkyl group substituted with halogen unless otherwise stated.

The term "heteroalkyl group" as used herein means that at least one of the carbon atoms constituting the alkyl group is replaced by a heteroatom.

The term "alkenyl group" or "alkynyl group ", as used herein, unless otherwise indicated, each have a double bond or triple bond of from 2 to 60 carbon atoms and include straight chain or branched chain groups, It is not.

The term "cycloalkyl" as used herein, unless otherwise specified, means alkyl which forms a ring having from 3 to 60 carbon atoms, but is not limited thereto.

The term "alkoxyl group "," alkoxy group ", or "alkyloxy group" used in the present invention means an alkyl group to which an oxygen radical is attached and, unless otherwise stated, has a carbon number of 1 to 60, It is not.

The term "alkenoyl group "," alkenoyl group ", "alkenyloxy group ", or" alkenyloxy group "as used in the present invention means an alkenyl group to which an oxygen radical is attached, , But is not limited thereto.

As used herein, the term "aryloxyl group" or "aryloxy group" refers to an aryl group attached to an oxygen radical and, unless otherwise stated, has a carbon number of 6 to 60, but is not limited thereto.

The terms "aryl group" and "arylene group ", as used herein, unless otherwise specified, each have 6 to 60 carbon atoms, but are not limited thereto. In the present invention, an aryl group or an arylene group means a single ring or a multicyclic aromatic group, and neighboring substituents include aromatic rings formed by bonding or participating in the reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracenyl group, a fluorene group, a spirobifluorene group, or a spirobifluorene group.

The prefix "aryl" or "ar" means a radical substituted with an aryl group. For example, the arylalkyl group is an alkyl group substituted with an aryl group, the arylalkenyl group is an alkenyl group substituted with an aryl group, and the radical substituted with an aryl group has the carbon number described in the present specification.

Also, if prefixes are named consecutively, it means that the substituents are listed in the order listed first. For example, the arylalkoxy group means an alkoxy group substituted with an aryl group, the alkoxycarbonyl group means a carbonyl group substituted with an alkoxyl group, and in the case of an arylcarbonylalkenyl group, an alkenyl group substituted with an arylcarbonyl group means Wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.

The term "heteroalkyl ", as used herein, unless otherwise indicated, means an alkyl comprising one or more heteroatoms. The term "heteroaryl group" or "heteroarylene group" as used in the present invention means an aryl or arylene group having 2 to 60 carbon atoms each containing at least one heteroatom unless otherwise specified, And includes at least one of a single ring and a multi-ring, and neighboring functional devices may be formed in combination.

The term "heterocyclic group ", as used herein, unless otherwise indicated, includes one or more heteroatoms, has from 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings and includes a heteroaliphatic ring and hetero Aromatic rings. Adjacent functional groups may be combined and formed.

As used herein, the term "heteroatom " refers to N, O, S, P or Si unless otherwise stated.

The "heterocyclic group" may also include a ring including SO2 instead of the carbon forming the ring. For example, the "heterocyclic group" includes the following compounds.

Unless otherwise stated, the term "aliphatic" as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms and an "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.

Unless otherwise specified, the term "ring" as used herein refers to a fused ring consisting of an aliphatic ring of 3 to 60 carbon atoms or an aromatic ring of 6 to 60 carbon atoms or a heterocycle of 2 to 60 carbon atoms, or combinations thereof, Saturated or unsaturated ring.

Other hetero-compounds or hetero-radicals other than the above-mentioned hetero-compounds include, but are not limited to, one or more heteroatoms.

Unless otherwise specified, the term "carbonyl" as used herein refers to -COR ', wherein R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, A cycloalkyl group of 2 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or a combination thereof.

Unless otherwise indicated, the term "ether" used in the present invention refers to -RO-R 'wherein R or R' are each independently of the other hydrogen, an alkyl group of 1-20 carbon atoms, An aryl group, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

One also no explicit description, the terms in the "unsubstituted or substituted", "substituted" is heavy hydrogen, a halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C for use in the present invention ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl amine group, C ₁ ~ C ₂₀ alkyl thiophene group, C ₆ ~ C ₂₀ aryl thiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C of ₂₀ alkynyl, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₈ ~ C ₂₀ aryl alkenyl group, a silane group, a boron Means a group substituted with at least one substituent selected from the group consisting of a halogen atom, a halogen atom, a cyano group, a germanium group, and a C ₂ to C ₂₀ heterocyclic group.

Unless otherwise expressly stated, the formula used in the present invention is applied in the same manner as the definition of the substituent by the definition of the index of the following formula.

When a is an integer of 0, substituent R ¹ is absent. When a is an integer of 1, one substituent R ¹ is bonded to any one of carbon atoms forming a benzene ring, and when a is an integer of 2 or 3 each coupled as follows: and wherein R ¹ may be the same or different from each other, a is the case of 4 to 6 integer, and bonded to the carbon of the benzene ring in a similar way, while the display of the hydrogen bonded to the carbon to form a benzene ring Is omitted.

1 is an illustration of an encapsulated device in accordance with an embodiment of the present invention.

Referring to FIG. 1, a first electrode 120, a second electrode 180, and a second electrode 180 formed on a substrate 110 are formed between the first electrode 110 and the second electrode 180, And an organic material layer. In this case, the first electrode 120 may be an anode and the second electrode 180 may be a cathode (cathode). In case of an inverting type, the first electrode may be a cathode and the second electrode may be an anode.

The organic material layer may include a hole injecting layer 130, a hole transporting layer 140, a light emitting layer 150, an electron transporting layer 160, and an electron injecting layer 170 sequentially on the first electrode 120. At this time, the remaining layers except the light emitting layer 150 may not be formed. An electron blocking layer, a light emitting auxiliary layer 151, a buffer layer 141, and the like, and the electron transport layer 160 may serve as a hole blocking layer.

In addition, although not shown, the organic EL device 200 according to the present invention may include a protective layer or a light-efficiency-improvement layer (not shown) formed on one surface of the first electrode 120 and the second electrode 180, Capping layer).

The organic electroluminescent device 200 according to an embodiment of the present invention can be manufactured using a physical vapor deposition (PVD) method. For example, a first electrode 120 is formed by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, and a hole injecting layer 130, a hole transporting layer 140, a light emitting layer 150, A transport layer 160 and an electron injection layer 170, and then depositing a material usable as the second electrode 180 on the organic layer.

In addition, the organic material layer may be formed using a variety of polymer materials, not a vapor deposition method, or a solution process or a solvent process such as a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, It is possible to produce a smaller number of layers by a method such as a dipping process, a screen printing process, or a thermal transfer process. Since the organic material layer according to the present invention can be formed by various methods, the scope of the present invention is not limited by the forming method.

The organic electroluminescent device 200 according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.

WOLED (White Organic Light Emitting Device) has advantages of high resolution realization and fairness, and can be manufactured using existing color filter technology of LCD. Various structures for a white organic light emitting device mainly used as a backlight device have been proposed and patented. Typically, a stacking method in which R (Red), G (Green) and B (Blue) light emitting parts are arranged side by side, and R, G and B light emitting layers are stacked up and down , And a color conversion material (CCM) method using photo-luminescence of an inorganic phosphor by using electroluminescence by a blue (B) organic light emitting layer and light from the electroluminescent material. Can be applied to such WOLED.

The organic electroluminescent device 200 according to the present invention may be one of an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a monochromatic or white illumination device.

Another embodiment of the present invention may include an electronic device including a display device including the above-described organic electroluminescent device 200 of the present invention and a control unit for controlling the display device. The electronic device may be a current or future wired or wireless communication terminal and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.

In addition, the present invention may further include a sealing layer 300 for protecting the organic EL device 200. 1, the sealing layer 300 is a single layer. However, the present invention is not limited thereto, and the sealing layer 300 may be formed of multiple layers. This configuration will be described with reference to FIG.

2 is a view schematically showing an example of the structure of an electronic device including an organic electroluminescent device. 2 includes a substrate 110, an organic electroluminescent device 200 disposed on the substrate 110, and an encapsulant layer 300 disposed on the organic electroluminescent device 200. In an electronic device according to an exemplary embodiment, the sealing layer 300 may be used to protect the organic electroluminescent device 200.

2, an embodiment in which the sealing layer 300 according to the present invention is composed of multiple layers composed of a first sealing layer 310 and a second sealing layer 320 is disclosed. 2, the sealing layer 300 has two layers. However, the sealing layer 300 may include two or more layers. When the sealing layer 300 is composed of two or more layers, it may include an inorganic barrier layer and an organic barrier layer. For example, when the first sealing layer 310 is an inorganic barrier layer, the second sealing layer 320 may be an organic barrier layer. When the first sealing layer 310 is an organic barrier layer, the second sealing layer 320 ) May be an inorganic barrier layer.

Further, as shown in Fig. 2, the sealing layer 300 of the present invention can be disposed on the device member. Specifically, the sealing layer 300 may be disposed on the organic EL device 200, and more specifically, the sealing layer 300 may be disposed on the organic EL device 200. That is, the sealing layer 300 can be disposed in a structure that can effectively protect the organic electroluminescent device 200. At this time, the sealing layer 300 has an effect of enhancing the reliability of the electronic device by blocking moisture and oxygen in the organic EL device 200. The sealing composition constituting the sealing layer 300 includes the compound represented by the following formula (1), and the above-mentioned effect can be exhibited.

Hereinafter, the compound according to one aspect of the present invention will be described. A compound according to one aspect of the present invention is represented by the following formula (1).

In Formula 1,

1) a, b, c, d, e, f, g and h are integers of 0 or 1;

(Wherein a, b, c, d, e, f, g and h may be the same or different.)

2) X ¹ to X ⁵ are each independently of one another O, S, NR 'and CR'R ";

Wherein R 'and R "are independently of each other a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₄ aryl group, or a C ₂ -C ₂₀ heteroaryl group, and R' and R" It can be formed and bound to a spy.)

3) Ar ¹ and Ar ² are each a C ₆ -C ₂₄ arylene group;

4) R ¹ , R ² , R ⁴ and R ⁵ are C ₂ -C ₂₀ alkylene groups;

5) R ³ and R ⁶ are each the same or different and are one of hydrogen and a C ₁ -C ₂₀ alkyl group;

6) n may be an integer of 0 or 1.

When each of X ¹ to X ⁵ , Ar ¹ , Ar ² , and R ¹ to R ⁶ is an alkyl group, an aryl group, a heteroaryl group, an arylene group, or an alkylene group, halogen; A silane group substituted or unsubstituted with an alkyl group having _{1 to 20} carbon atoms or an aryl group having _{6 to 20} carbon atoms; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ -C ₂₀ ; A C ₁ -C ₂₀ alkoxyl group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₆ -C ₂₀ aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A C ₃ -C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ -C ₂₀ ; And an arylalkenyl group having from _{8 to 20} carbon atoms.

The aryl group may be an aryl group having 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, and the heterocyclic group may have 2 to 60 carbon atoms, preferably 2 carbon atoms More preferably 1 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and in the case of the alkyl group, the number of carbon atoms is 1 to 50, preferably 1 to 30, more preferably 1 to 20, May be an alkyl group of 1 to 10 carbon atoms.

Specifically, when the aryl group or the arylene group is the aryl group or the arylene group, the aryl group or the arylene group may be independently selected from the group consisting of a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthryl group or a phenylene group, a biphenylene group, Or a phenanthrylene group.

More specifically, the compound represented by Formula 1 may be any one of the following compounds, but the compound represented by Formula 1 is not limited to the following compounds.

In the above Chemical Formulas 2 to 6,

n, X ¹ to X ⁵ , Ar ¹ , Ar ² , and R ¹ to R ⁶ are the same as defined in Formula 1 above.

More specifically, the compound represented by Formula 1 may be any one of the following compounds, and the compound represented by Formula 1 is not limited to the following compounds.

The sealing composition using the compound of Formula 1 of the present invention can form an organic barrier layer positioned between inorganic barrier layers for encapsulating or encapsulating a flexible display device, and the organic barrier layer photo- .

The sealing composition (organic barrier layer material) can be applied by a method such as vapor deposition, spin coating, or slit coating, and an initiator can be used for photo-curing.

The initiator may include, without limitation, conventional photopolymerization initiators capable of carrying out photo-curable reactions. For example, the photopolymerization initiator may include triazine, acetophenone, benzophenone, thioxanthone, benzoin, phosphorus, oxime, or a mixture thereof.

Examples of triazine derivatives include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxysti (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho- Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho-1-yl) -4,6- (Piperonyl) -6-triazine, 2,4- (trichloromethyl (4'-methoxystyryl) -6-triazine or mixtures thereof.

Examples of the acetophenone-based solvents include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-butyldichloro 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1-one, 2,2'-dichloroacetophenone, Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, or mixtures thereof.

Examples of the benzophenone-based compounds include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-dichlorobenzo Phenone, 3,3'-dimethyl-2-methoxybenzophenone, or a mixture thereof.

Examples of thioxanthone include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone or And mixtures thereof.

The benzoin group may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal or a mixture thereof.

Phosphorous can be bisbenzoylphenylphosphine oxide, benzoyldiphenylphosphine oxide or mixtures thereof.

The oxime system was prepared by reacting 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and 1- (o-acetyloxime) 2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, or mixtures thereof.

The initiator may be included in the composition in an amount of 0.1 to 20 wt%, preferably 0.5 to 20 wt%, more preferably 0.5 to 10 wt%, and most preferably 0.5 to 7 wt%, based on the solid content. In the above range, photopolymerization can sufficiently take place at the time of exposure, and the transmittance can be prevented from being lowered due to the unreacted initiator remaining after the photopolymerization.

Formation of the organic barrier layer using photocuring is performed by coating the composition for sealing at 0.1 to 20 μm, preferably 1 to 15 μm, most preferably 1 to 10 μm, at 10 to 500 mW / cm 2 for 1 second to 60 seconds It can be cured. At this time, the curing rate may be 90% or more, preferably 93% or more. At this time, the composition and the initiator not participating in the photo-curing reaction in the organic barrier layer are minimized and the pass-way of moisture and / or oxygen is suppressed, so that good barrier properties can be obtained.

Also, when the sealing composition is cured (when an organic barrier layer is formed), the coated sealing composition may shrink, and the shrinkage may be about 1 to 20%, more preferably about 1 to 15% Can be.

When the shrinkage ratio of the organic barrier layer is 20% or more, dark spots and pixel shrinkage occur due to oxygen and / or moisture penetration in the inorganic barrier layer. In addition, The occurrence of warpage in the formation of the multilayer barrier layer can lead to the bonding of the light emitting element.

The inorganic barrier layer and the organic barrier layer may be deposited by sputtering, chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD), evaporation, sublimation, ink jet, and combinations thereof.

The multi-layer barrier layer includes the organic barrier layer and the inorganic barrier layer, but may be alternately deposited, the number of barrier layers is not limited, and the number of barrier layers may be selected from the group consisting of oxygen and / or moisture and / It can be changed according to the level. The organic barrier layer and the inorganic barrier layer may be alternately deposited in two or more layers and 10 layers or less, preferably 2 layers or more and 7 layers or less.

That is, the sealing layer according to the present invention may be disposed on a member for an apparatus of an electronic device including an organic electroluminescent device, and may be composed of a multi-layered barrier layer including an inorganic barrier layer and an organic barrier layer. Wherein the inorganic barrier layer comprises a metal, a metal oxide, a metal nitride, a metal carbide, a metal oxynitride, a metal oxygen boride, or a mixture thereof, wherein the metal is selected from the group consisting of Si, Al, ), Zinc (Zn), antimony (Sb), indium (In), germanium (Ge), tin (Sn), bismuth (Bi), transition metals and lanthanide metals.

In another embodiment, the encapsulating composition of the present invention may contain the compound alone, or the compound may be contained in a combination of two or more different types, or the compound may be contained in combination with two or more kinds of other compounds. In other words, the sealing composition may contain the compound corresponding to formula (I) alone, and may include a mixture of two or more compounds of formula (I), and the compound of claim 1 to claim 3 and claims 9 to 10 , And a compound not corresponding to the present invention.

Herein, the compound not corresponding to the present invention may be a single compound or may be two or more compounds. When the compound is contained in combination with two or more kinds of other compounds, the other compound may be a known compound of each organic layer or a compound to be developed in the future. At this time, the compound contained in the organic material layer may be composed of the same kind of compound, but it may be a mixture of two or more different kinds of compounds represented by the general formula (1). When the encapsulating composition contains two or more compounds of formula (I), the compound of formula (I) may contain 50 to 95% by weight (based on the total weight of two or more compounds) based on the solid content.

Meanwhile, the sealing composition according to the present invention may be mixed with at least one compound of the formula (1) and a compound represented by the formula (7), and the formula (7) is as follows.

In Formula 7,

1) P is an integer from 1 to 20;

2) X ₁ and X ₂ are each the same or different and are one of O, S and NR ';

(Wherein R 'is any _one of a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₄ aryl group, and a C ₂ -C ₂₀ heteroaryl group.)

3) Y ₁ and Y ₂ are the same or different and each represents an alkylene group of C ₁ -C ₂₀ , an arylene group of C ₆ -C _24, an arylalkylene group of C ₇ -C ₂₄ , a C ₁ -C ₂₀ alkyl A phenoxy group;

4) R ₃ and R ₆ are the same or different from each other and are one of hydrogen and a C ₁ -C ₂₀ alkyl group;

5) R ₇ , R ₈ and R ₉ are any one of hydrogen, deuterium, tritium, C ₁ -C ₃₀ alkyl, C ₁ - ₂₀ alkoxy, and hydroxyl.

Wherein X ₁ , X ₂ , Y ₁ , Y ₂ , R ₃ , R ₆ , R ₇ , R ₈ and R ₉ are independently selected from the group consisting of alkyl, aryl, heteroaryl, alkylene, arylene, , An alkoxy group, a hydroxy group, each of which may be substituted with deuterium; halogen; A silane group substituted or unsubstituted with an alkyl group having _{1 to 20} carbon atoms or an aryl group having _{6 to 20} carbon atoms; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ -C ₂₀ ; A C ₁ -C ₂₀ alkoxyl group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₆ -C ₂₀ aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A C ₃ -C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ -C ₂₀ ; And an arylalkenyl group having from _{8 to 20} carbon atoms.

The aryl group may be an aryl group having 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, and the heterocyclic group may have 2 to 60 carbon atoms, preferably 2 carbon atoms More preferably 1 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and in the case of the alkyl group, the number of carbon atoms is 1 to 50, preferably 1 to 30, more preferably 1 to 20, May be an alkyl group of 1 to 10 carbon atoms.

Specifically, when the aryl group or the arylene group is the aryl group or the arylene group, the aryl group or the arylene group may be independently selected from the group consisting of a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthryl group or a phenylene group, a biphenylene group, Or a phenanthrylene group.

More specifically, the compound represented by the formula (7) may be any one of the following compounds, but the compound represented by the formula (7) is not limited to the following compounds.

When the encapsulating composition contains two or more compounds represented by formula (I), the compound of formula (1) contains 50 to 95% by weight (total weight% of two or more compounds) based on solids, 1 to 40% To 20% by weight, but the present invention is not limited thereto. Hereinafter, the synthesis examples of the compound represented by the formula (1) and the production example of the organic electroluminescence device according to the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples.

[ Synthetic example ]

The compounds according to the invention (final products) are synthesized by the following reaction schemes, but are not limited thereto.

<Reaction Scheme 1>

Examples of the synthesis of specific compounds are as follows.

1. P1-1 Synthetic example

<Reaction Scheme 2>

The starting material, 1- (bromomethyl) -3-phenoxybenzene (10 g, 38.00 mmol) and acrylic acid (2.73 g, 38.00 mmol) were dissolved in acetonitrile (190 ml) in a round bottom flask, and then triethylamine (11.53 g, 114.00 mmol ) Was added and stirred at 80 ° C. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and water, and the organic layer was washed with MgSO ₄ Dried and concentrated. The concentrated compound was subjected to silica gel column chromatography to obtain 5.79 g (yield 70%) of the product.

2. P1-6 Synthetic example

<Reaction Scheme 3>

(1.00 g, 27.22 mmol) and acrylic acid (1.96 g, 27.22 mmol) were dissolved in Acetonitrile (140 ml) in a round bottom flask, Triethylamine (8.26 g, 81.66 mmol) was obtained as a product (6.19 g, 62% yield) using the above-mentioned P1-4 synthesis method.

3. P1-19 Synthetic example

<Reaction Scheme 4>

(1.00 g, 26.87 mmol) and acrylic acid (1.93 g, 26.87 mmol) were dissolved in acetonitrile (140 ml) in a round bottom flask and then triethylamine (8.15 g, 80.67 mmol) mmol) was obtained 7.59 g (yield 83%) of the product using the above-mentioned P1-1 synthesis method.

4. P1-23 Synthetic example

<Reaction Scheme 5>

The starting material, bis (4 - ((2-bromoethyl) thio) phenyl sulfane (10.00 g, 21.53 mmol) and acrylic acid (1.55 g, 21.53 mmol) were dissolved in Acetonitrile (170 ml) 6.53 g, 64.56 mmol) was used to obtain 5.48 g (yield 57%) of the product using the above P1-1 synthesis method.

5. P1-25 Synthetic example

<Reaction Scheme 6>

Triethylamine (8.82 g, 87.18 mmol) was dissolved in acetonitrile (150 ml) in a round bottom flask and bis (3-bromophenyl) sulfane (10.00 g, 29.06 mmol) Using the P1-1 synthesis method, 6.73 g (yield 71%) of the product was obtained.

6. P1-33 Synthetic example

<Reaction Scheme 7>

(1.00 g, 23.19 mmol) and acrylic acid (1.67 g, 23.19 mmol) were dissolved in acetonitrile (120 ml) in a round bottom flask, , And then 8.53 g (yield: 89%) of the product was obtained using Triethylamine (7.03 g, 69.57 mmol) using the above-mentioned P1-1 synthesis method.

7. P1-51 Synthetic example

<Reaction Scheme 8>

Acetonitrile (150 ml) was added to the round bottom flask with the starting material (2-bromoethyl) (3- (2-phenylpropan-2-yl) phenyl) sulfane (10.00 g, 29.82 mmol) . Triethylamine (9.05 g, 89.46 mmol) was then dissolved in 8.01 g (83% yield) of the product using the synthesis of P1-1.

8. P2-3 Synthetic example

<Reaction Scheme 9>

The starting material, 1,5-dibromopentane (10.00 g, 43.48 mmol) and acrylic acid (6.26 g, 86.96 mmol) were dissolved in acetonitrile (220 ml) in a round bottom flask. Triethylamine (13.19 g, 130.44 mmol) -1 &lt; / RTI &gt; synthesis method was used to obtain 5.62 g (yield 61%) of the product.

9. P2-6 Synthetic example

<Reaction formula 10>

Triethylamine (9.24 g, 91.41 mmol) was dissolved in Acetonitrile (150 ml) in a round-bottomed flask, and then the above P1 -1 &lt; / RTI &gt; synthesis method was used to obtain 8.04 g (yield: 85%) of the product.

10. P2-8 Synthetic example

<Reaction Scheme 11>

Triethylamine (9.24 g, 91.41 mmol) was dissolved in Acetonitrile (150 ml) in a round-bottomed flask, and then the above P1 -1 &lt; / RTI &gt; synthesis method was used to obtain 4.81 g (yield 51%) of the product.

* 11. P2-9 Synthesis Example

<Reaction Scheme 12>

The starting material, 2,6-dibromoheptane (10.00 g, 38.75 mmol) and prop-2-enethioic S-acid (6.82 g, 77.50 mmol) were dissolved in acetonitrile (190 ml) 116.25 mmol) was obtained 7.70 g (yield 73%) of the product using the above-mentioned P1-1 synthesis method.

12. P2-16 Synthetic example

<Reaction Scheme 13>

The starting material, 1,3-dibromo-2-propoxypropane (10.00 g, 38.46 mmol) and acrylic acid (5.54 g, 76.93 mmol) were dissolved in acetonitrile (190 ml) in a round bottom flask and then triethylamine (11.65 g, 115.38 mmol ) Of the product was obtained using 6.5 g (yield: 70%) of the product.

13. P2-17 Synthetic example

<Reaction Scheme 14>

Acrylate (4.06 g, 56.48 mmol) and acrylic acid (4.06 g, 56.48 mmol) were dissolved in acetonitrile (140 ml) in a round bottom flask and then triethylamine (8.57 g, 84.72 mmol ) Was obtained 6.64 g (yield 70%) of the product using the above-mentioned P1-1 synthesis method.

On the other hand, the synthesis example of the present invention represented by the formula (1) is described in Org . Lett . , 2009, 11 (20), 4708-4711, J. Org . Chem . , 2001, 66 (7), 2291-2295, Org . Lett . , 2005, 7 (7), 1295-1298, J. Org . Chem . , 2008, 73 (19), 7772-7774, Organometallics 2002, 21 (26), 5713-5725, J. Org . Chem . , 2011, 76 (7), 2187-2194, J. Am. Chem . Soc . , 2009, 131 (5), 1766-1774, etc., and other substituents (X ₁ to X ₅ , Ar ¹ , Ar ² , R ₁ to R ₆ ) defined in Chemical Formula 1 are bonded in addition to the substituent Those skilled in the art will readily understand that the reaction proceeds.

Evaluation of Manufacture of Sealing Composition

[ Example ] Preparation of mixed composition

A mixture of a compound of Formula 1 (P1-1 to P1-55) and Formula 7 (P2-1 to P2-21) of the present invention and a mixture of initiator Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (diphenyl 2, 4, 6-trimethylbenzoyl) phosphine oxide, Darocur TPO) were mixed as shown in Table 1 below to prepare a composition. At this time, the initiator Darocur TPO uses 3% by weight. (Total weight of the total mixture composition is 100%). The initiator is Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, Darocur TPO) Lt; / RTI &gt;

As a comparative example, a composition was prepared by mixing Darocur TPO, which is an initiator, with a mixture of a compound of the present invention and a comparative compound or a mixture of comparative compounds as shown in Table 1 below. The initiator, Darocur TPO, uses 3% by weight. Specifically, the compounds used in the comparative examples were Comparative Compounds 1 to 3, and Comparative Compounds 1 to 3 were trimethylolpropane triacrylate (trimethylolpropane triacrylate (Dipentaerythritol hexaacrylate, Miramer M600) and Poly (ethylene glycol) diacrylate (polyethylene glycol diacrylate, Miramer M284).

  [Comparative Compound 1] [Comparative Compound 2] [Comparative Compound 3]

The above-mentioned mixed composition was mixed in the contents (by weight) shown in Table 1 below and stirred for 3 hours to prepare a composition for sealing.

P1-1 P1-21 P2-5 P2-7 P2-20 P2-21 compare
Compound 1 compare
Compound 2 compare
Compound 3 Example 1 80% 17% Example 2 80% 17% Example 3 80% 17% Example 4 80% 17% Example 5 80% 10% 7% Comparative Example 1 80% 17% Comparative Example 2 80% 17% Comparative Example 3 80% 17% Comparative Example 4 17% 80% Comparative Example 5 80% 10% 7%

The curing shrinkage, light-curing rate, and light transmittance of the compositions mixed according to the contents of Table 1 were measured in the following manner, and the results are shown in Table 2 below.

1. Cure shrinkage

The specific gravity of the liquid composition and the specific gravity of the solid after curing were measured by digital solid viscometer DME-220E (Shinko, Japan), and the hardening shrinkage ratio was calculated. The film was coated with a composition of 10um? 2um and then UV cured (100mW / cm2x10 sec) to prepare a film (thickness: 8-12um, width 1.5-2.5cm, length 1.5-2.5cm). The hardening shrinkage ratio was calculated according to the following formula 3.

[Formula 3]

Cure shrinkage ratio (%) = (solid specific gravity after curing-specific gravity of liquid composition before curing) / specific gravity of liquid composition before curing x 100

2. Light curing rate

The intensity of absorption peak in the ^first vicinity (C = O) was measured ^- 1635cm-1 near the (C = C), 1720cm using FT-IR (FT / IR- 6600, Jasco , Inc.) with respect to the photocurable composition. A 20 cm x 20 cm x 3 m (width x length x thickness) specimen was obtained by applying a photocurable composition on a glass substrate by spraying and irradiating it at 100 J / cm &lt; ² &gt; for 10 seconds to UV cure to obtain FT-IR (NICOLET 4700, Thermo The intensity of the absorption peak at around 1635 cm ^-1 (C = C) and around 1720 cm ^-1 (C = O) was measured using a spectrophotometer The photo-curing rate was calculated according to the following equation (4).

[Formula 4]

Photocuring rate (%) = | 1- (A / B) | x 100

(Wherein, A is the ratio of the intensity of the absorption peak of 1635cm ^-1 in the vicinity of the intensity of the absorption peak in the vicinity of 1720cm ^-1 for the cured film, B is in the vicinity of 1720cm ^-1 for the photocurable composition The ratio of the intensity of the absorption peak at around 1635 cm &lt; ^-1 &gt; to the intensity of the absorption peak)

3. Light Transmittance

A film having a thickness of 10 占 퐉 was prepared by UV-curing the composition for encapsulation, and the light transmittance of the film was measured with a Lambda 950 (Perkin Elmer) at a wavelength of 550 nm in a visible light region.

Cure shrinkage (%) Light curing rate (%) Light transmittance (%) Ohnishi parameter Example 1 11.5 96 96.5 2.67 Example 2 14.9 90 93.3 2.77 Example 3 9.9 94 93.5 2.63 Example 4 13.5 93 94.1 2.74 Example 5 9.8 96 96.2 2.55 Comparative Example 1 21.5 87 89.5 4.17 Comparative Example 2 22.3 78 90.7 4.77 Comparative Example 3 19.8 82 90.1 4.25 Comparative Example 4 18.8 85 91.2 5.83 Comparative Example 5 23.3 90 91.5 4.20

As a result of confirming Table 2, Examples 1 to 5, which are compositions containing the compound of the present invention, have low shrinkage and high light curability and excellent results in light transmittance. The calculated Ohnishi parameter values showed high plasma resistivity.

This can be explained by the correlation between each rate and the Ohnishi parameter. The larger the value of the Ohnishi parameter is in the range of 2 to 7, the faster the etch rate, and the faster the etch rate is, The plasma resistance is lowered.

The ohnishi parameter values of Examples 1 to 5 using the composition of the present invention are smaller than those of Comparative Examples 1 to 5, Resistance. &Lt; / RTI &gt;

110: substrate
200: organic electroluminescent device
300: sealing layer

Claims (10)

And at least one compound represented by the following general formula (1) and at least one compound represented by the following general formula (7), and is disposed on the organic light emitting device and used as a sealing material to prevent moisture and oxygen penetration into the organic light emitting device Wherein the organic electroluminescence device is a light emitting diode.

1) X ¹ to X ⁵ are each independently equal or different and are one of O, S, NR 'and CR'R ";
Wherein R 'and R "are each independently of the other and are selected from the group consisting of a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₄ aryl group, and a C ₂ -C ₂₀ heteroaryl group, and R'Quot; R "can form a ring and bind to a spy.)
2) Ar ¹ and Ar ² are each independently the same or different and are C ₆ -C ₂₄ arylene groups;
3) R ¹ , R ² , R ⁴ and R ⁵ are each independently of the other a C ₁ -C ₂₀ alkylene group;
4) R ³ and R ⁶ are each independently of one another either the same or different and are hydrogen and a C ₁ -C ₂₀ alkyl group;
5) n may be an integer of 0 or 1,
6) a, b, c, d, e, f, g and h are each independently selected from an integer of 0 or 1,
N is 0 when n, a, b, c, d, e, f, g,
when one of f, or h is 1 and n is 1, X ¹ is selected from any one of S, NR ', and CR'R ", wherein a, c, e, and g are 0 and b or d is 1; )
7) P is an integer from 5 to 20;
8) X ₁ and X ₂ are each the same or different and are one of O, S and NR ';
(Wherein R 'is any _one of a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₄ aryl group, and a C ₂ -C ₂₀ heteroaryl group.)
9) Y ₁ and Y ₂ are the same or different and each represents an alkylene group of C ₁ -C ₂₀ , an arylene group of C ₆ -C _24, an arylalkylene group of C ₇ -C ₂₄ , a C ₁ -C ₂₀ alkyl A phenoxy group;
10) R ₇ , R ₈ and R ₉ are any one of hydrogen, deuterium, tritium, C ₁ -C ₃₀ alkyl, C ₁ -C ₂₀ alkoxy, and hydroxyl.
Wherein X ¹ to X ⁵ , Ar ¹ , Ar ² , R ¹ to R ⁹ , X ₁ , X ₂ , Y ₁ and Y ₂ represent an alkyl group, an aryl group, An alkylene group, an alkyleneoxy group, an alkoxy group, or a hydroxy group, each of these may be substituted with deuterium; halogen; A silane group substituted or unsubstituted with an alkyl group having _{1 to 20} carbon atoms or an aryl group having _{6 to 20} carbon atoms; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ -C ₂₀ ; A C ₁ -C ₂₀ alkoxyl group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₆ -C ₂₀ aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A C ₃ -C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ -C ₂₀ ; And an arylalkenyl group having from _{8 to 20} carbon atoms. The method according to claim 1,
The composition for encapsulating an organic electroluminescence device according to claim 1, wherein the compound represented by the formula (1) is represented by the following formulas (2) to (6).

In the above Chemical Formulas 2 to 6,
n, X ¹ to X ⁵ , Ar ¹ , Ar ² , and R ¹ to R ⁶ are the same as defined in Formula 1 above. The method according to claim 1,
(1) is one of the following compounds.

The method according to claim 1,
The encapsulating composition for an organic electroluminescent device according to claim 1, wherein the encapsulating composition further comprises an initiator. 5. The method of claim 4,
2. The encapsulating composition for an organic electroluminescent device according to claim 1, wherein the compound represented by the formula (1) is a mixture of two or more different compounds. The method according to claim 1,
(7) is one of the following compounds.

The method according to claim 1,
In the case where the above formula (1) is two or more, the formula (1) is 50 to 95% by weight based on the solid content, 2 to 40% Wherein the organic electroluminescence device is a light emitting diode. 5. The method of claim 4,
The composition according to claim 1, wherein the composition comprises 70 to 80% by weight of a compound represented by the formula (I) and 0.1 to 20% by weight of an initiator. A member for a device; And
And a multilayer barrier layer disposed on the device member and comprising an inorganic barrier layer and an organic barrier layer,
Wherein the organic barrier layer comprises the encapsulating composition of any one of claims 1 to 9. 10. The method of claim 9,
Wherein the inorganic barrier layer comprises a metal, a metal oxide, a metal nitride, a metal carbide, a metal oxynitride, a metal oxygen boride, or a mixture thereof, wherein the metal is selected from the group consisting of Si, Al, And at least one of zinc (Zn), antimony (Sb), indium (In), germanium (Ge), tin (Sn), bismuth (Bi), transition metals and lanthanide metals.

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