Compound for organic optoelectronic element, composition for organic optoelectronic element, organic optoelectronic element and display device

Abstract

The present invention relates to a compound for an organic photoelectric element represented by Chemical Formula 1, a composition for an organic photoelectric element, an organic photoelectric element, and a display device, the composition comprising the compound represented by Chemical Formula 1. The description of Chemical Formula 1 is as defined in the specification.

Description

Technical Field

[0001] Disclosed are a compound for an organic photoelectric element, a composition for an organic photoelectric element, an organic photoelectric element and a display device. Background Art

[0002] An organic photoelectric element (organic photodiode) is an element that can convert electrical energy and light energy into each other.

[0003] Organic photoelectric elements can be roughly divided into two types according to the operating principle: one is a photoelectric element that generates electric energy by separating excitons formed by light energy into electrons and holes and transferring the electrons and holes to different electrodes, respectively; the other is a light-emitting element that generates light energy from electric energy by supplying voltage or current to electrodes.

[0004] Examples of the organic optoelectronic element include an organic optoelectronic element, an organic light emitting diode, an organic solar cell, and an organic photosensitive drum.

[0005] Among them, organic light emitting diodes (OLEDs) have attracted much attention in recent years due to the increasing demand for flat panel display devices. Organic light emitting diodes are components that convert electrical energy into light, and the performance of organic light emitting diodes is greatly affected by the organic material between the electrodes. Summary of the invention

[0006] [Technical issues]

[0007] One embodiment provides a compound for an organic photoelectric element, which can realize an organic photoelectric element with high efficiency and long lifetime.

[0008] Another embodiment provides a composition for an organic photoelectric element, which includes the compound for an organic photoelectric element.

[0009] Another embodiment provides an organic photoelectric element including the compound for an organic photoelectric element or the composition for an organic photoelectric element.

[0010] Another embodiment provides a display device including an organic photoelectric element.

[0011] [Technical solution]

[0012] According to an embodiment, a compound for an organic photoelectric element represented by Chemical Formula 1 is provided.

[0013] [Chemical formula 1]

[0014]

[0015] In Chemical Formula 1,

[0016] R 1 To R3 are independently hydrogen, deuterium, cyano, or substituted or unsubstituted C1 to C10 alkyl,

[0017] n is an integer from 0 to 2, and

[0018] Ar 1 and Ar 2 are independently substituted or unsubstituted C6 to C30 aryl,

[0019] When n is 0, excluding Ar 1 and Ar 2 This is also the case for unsubstituted phenyl.

[0020] According to another embodiment, a composition for an organic photoelectric element includes the aforementioned compound for an organic photoelectric element (hereinafter referred to as "the first compound for an organic photoelectric element") and a second compound for an organic photoelectric element represented by Chemical Formula 2.

[0021] [Chemical formula 2]

[0022]

[0023] In chemical formula 2,

[0024] Y 1 and Y 2 are independently substituted or unsubstituted C6 to C20 aryl, or substituted or unsubstituted C2 to C30 heterocyclic,

[0025] L 1 and L 2 are independently a single bond, or a substituted or unsubstituted C6 to C20 arylene group,

[0026] R a and R 4 To R 7 and R and R are independently hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, or substituted or unsubstituted C2 to C30 heterocyclyl.

[0027] m is an integer from 0 to 2.

[0028] According to another embodiment, an organic photoelectric element includes an anode and a cathode facing each other and at least one organic layer between the anode and the cathode, and the organic layer includes a compound for an organic photoelectric element or a composition for an organic photoelectric element.

[0029] According to another embodiment, a display device including an organic photoelectric element is provided.

[0030] [Beneficial Effects]

[0031] High-efficiency and long-life organic photoelectric devices can be realized. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 and Figure 2 are cross-sectional views each showing an organic light emitting diode according to an embodiment.

[0033] <symbol description>

[0034] 100, 200: Organic light-emitting diodes

[0035] 105: Organic layer

[0036] 110: cathode

[0037] 120: Anode

[0038] 130: Luminous layer

[0039] 140: Hole auxiliary layer DETAILED DESCRIPTION

[0040] Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, the present invention is not limited thereto, and the present invention is defined by the scope of the claims.

[0041] In the present specification, when no limitation is otherwise provided, "substituted" means that at least one hydrogen of a substituent or a compound is replaced by deuterium, halogen, hydroxyl, amino, substituted or unsubstituted C1 to C30 amine, nitro, substituted or unsubstituted C1 to C40 silyl, C1 to C30 alkyl, C1 to C10 alkylsilyl, C6 to C30 aralkyl, C3 to C30 cycloalkyl, C3 to C30 heterocycloalkyl, C6 to C30 aryl, C2 to C30 heteroaryl, C1 to C20 alkoxy, C1 to C10 trifluoroalkyl, cyano or a combination thereof.

[0042] In one embodiment of the present invention, "substituted" refers to the replacement of at least one hydrogen in a substituent or compound by deuterium, C1 to C30 alkyl, C1 to C10 alkylsilyl, C6 to C30 aralkyl, C3 to C30 cycloalkyl, C3 to C30 heterocycloalkyl, C6 to C30 aryl, or C2 to C30 heteroaryl. In addition, in a specific embodiment of the present invention, "substituted" refers to the replacement of at least one hydrogen in a substituent or compound by deuterium, C1 to C20 alkyl, C6 to C30 aryl, or C2 to C30 heteroaryl. In addition, in a specific embodiment of the present invention, "substituted" refers to the replacement of at least one hydrogen in a substituent or compound by deuterium, C1 to C5 alkyl, C6 to C18 aryl, or cyano. In addition, in a specific embodiment of the present invention, "substituted" refers to the replacement of at least one hydrogen in a substituent or compound by deuterium, cyano, methyl, ethyl, propyl, butyl, phenyl, biphenyl, terphenyl, or naphthyl.

[0043] In the present specification, when a definition is not otherwise provided, "hetero" means that one functional group includes 1 to 3 hetero atoms selected from N, O, S, P and Si and the remainder is carbon.

[0044] In the present specification, "aryl group" refers to a group including at least one hydrocarbon aromatic part, and may include a group in which all elements of the hydrocarbon aromatic part have a p-orbital forming a conjugation, such as phenyl, naphthyl, etc., a group in which two or more hydrocarbon aromatic parts may be connected by a σ bond, such as biphenyl, terphenyl, quaterphenyl, etc., and a group in which two or more hydrocarbon aromatic parts are directly or indirectly fused to provide a non-aromatic condensed ring, such as fluorenyl, etc.

[0045] Aryl groups can include monocyclic, polycyclic, or fused-ring polycyclic (ie, rings which share adjacent pairs of carbon atoms) functional groups.

[0046] "Heterocyclic group" is a general concept of heteroaryl, and may include at least one heteroatom selected from N, O, S, P and Si other than carbon (C) in a cyclic compound (such as an aryl group, a cycloalkyl group, a condensed ring thereof or a combination thereof). When the heterocyclic group is a condensed ring, the entire ring or each ring of the heterocyclic group may include one or more heteroatoms.

[0047] For example, "heteroaryl" refers to an aryl group including at least one heteroatom selected from N, O, S, P and Si. Two or more heteroaryls are directly connected by a sigma bond, or when the heteroaryl includes two or more rings, the two or more rings may be fused. When the heteroaryl is a fused ring, each ring may include one to three heteroatoms.

[0048] More specifically, the substituted or unsubstituted C6 to C30 aryl group may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted m-terphenyl group, a substituted or unsubstituted o-terphenyl group, a substituted or unsubstituted The invention may include, but is not limited to, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted perylene group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furanyl group, or a combination thereof.

[0049] More specifically, the substituted or unsubstituted C2 to C30 heterocyclic group may be a substituted or unsubstituted furanyl, a substituted or unsubstituted phenylthio, a substituted or unsubstituted pyrrolyl, a substituted or unsubstituted pyrazolyl, a substituted or unsubstituted imidazolyl, a substituted or unsubstituted triazolyl, a substituted or unsubstituted oxazolyl, a substituted or unsubstituted thiazolyl, a substituted or unsubstituted oxadiazolyl, a substituted or unsubstituted thiadiazolyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted pyrazinyl, a substituted or unsubstituted triazinyl, a substituted or unsubstituted benzofuranyl, a substituted or unsubstituted benzophenylthio , substituted or unsubstituted benzimidazolyl, substituted or unsubstituted indolyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazoline, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiazinyl, substituted or unsubstituted acridinyl, substituted or unsubstituted phenazinyl, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenoxazinyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophenyl, or a combination thereof, but are not limited thereto.

[0050] In this specification, hole characteristics refer to the ability to donate electrons to form holes when an electric field is applied, based on the highest occupied molecular orbital (HOMO) energy level, and the holes formed in the anode can be easily injected into the light-emitting layer and transported in the light-emitting layer due to conductive properties.

[0051] In addition, the electronic property refers to the ability to accept electrons when an electric field is applied, and the electrons formed in the cathode can be easily injected into the light-emitting layer and transported in the light-emitting layer due to conductive properties.

[0052] Hereinafter, a compound for an organic photoelectric element according to one embodiment is described.

[0053] The compound for an organic photoelectric element according to one embodiment is represented by Chemical Formula 1.

[0054] [Chemical formula 1]

[0055]

[0056] In Chemical Formula 1,

[0057] R 1 To R 3 are independently hydrogen, deuterium, cyano, or substituted or unsubstituted C1 to C10 alkyl,

[0058] n is an integer from 0 to 2, and

[0059] Ar 1 and Ar 2 are independently substituted or unsubstituted C6 to C30 aryl,

[0060] The condition is that when n is 0, Ar is excluded 1 and Ar 2 This is also the case for unsubstituted phenyl.

[0061] In the compound for an organic optoelectronic element represented by Chemical Formula 1, the 9-carbazolyl group is directly or indirectly connected to the triazine through the p-phenylene group, the 9-carbazolyl group includes a phenyl substituent at position 3, and the triazine group has a structure including an aryl substituent.

[0062] Since the 9-carbazolyl group is linked to the triazine through the p-phenylene group, the LUMO electron cloud expands, thereby lowering the LUMO energy level, further enhancing the electron injection ability and the electron transport ability, thereby lowering the driving voltage of the element including the compound.

[0063] Furthermore, since the 9-carbazolyl group includes a phenyl substituent at position 3 and the triazine group includes an aryl substituent, hole injection capability and hole transport capability are also enhanced to achieve a suitable charge balance in the light emitting layer, resulting in improved efficiency and lifetime of a device including the compound.

[0064] For example, n can be an integer of 0 or 1, and

[0065] For example, Chemical Formula 1 may be represented by Chemical Formula 1A or Chemical Formula 1B.

[0066]

[0067] In Chemical Formula 1A and Chemical Formula 1B, R 1 To R 3 ,Ar 1 and Ar 2 Same as above.

[0068] For example, Ar in Formula 1A 1 and Ar 2 One of the groups may be unsubstituted phenyl, and the other may be substituted phenyl, substituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted triphenylene, or substituted or unsubstituted fluorenyl.

[0069] For example, Ar in formula 1B 1 and Ar 2 and wherein the at least one radical is independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted triphenylene, or substituted or unsubstituted fluorenyl.

[0070] For example, Ar 1 and Ar 2 The groups may be independently selected from Group I.

[0071] [Group I]

[0072]

[0073] In Group I, * is the connection point.

[0074] In an example embodiment, Ar 1 and Ar 2 The groups may independently be substituted or unsubstituted phenyl groups, substituted or unsubstituted biphenyl groups, or substituted or unsubstituted terphenyl groups, but are not limited thereto.

[0075] In a specific embodiment, when n=0, Ar 1 and Ar 2 One of the groups may be an unsubstituted phenyl group, and the other may be a substituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted terphenyl group.

[0076] In addition, when n = 1, Ar 1 and Ar 2 The groups may independently be substituted or unsubstituted phenyl groups, substituted or unsubstituted biphenyl groups, or substituted or unsubstituted terphenyl groups.

[0077] For example, the compound for an organic photoelectric element may be one of the compounds selected from Group 1, but is not limited thereto.

[0078] [Group 1]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084] A composition for an organic photoelectric element according to another embodiment includes a compound for an organic photoelectric element (hereinafter, referred to as “a first compound for an organic photoelectric element”) and a second compound for an organic photoelectric element represented by Chemical Formula 2.

[0085] [Chemical formula 2]

[0086]

[0087] In chemical formula 2,

[0088] Y 1 and Y 2 are independently substituted or unsubstituted C6 to C20 aryl, or substituted or unsubstituted C2 to C30 heterocyclic,

[0089] L 1 and L 2 are independently a single bond, or a substituted or unsubstituted C6 to C20 arylene group,

[0090] R a and R 4 To R 7 and R and R are independently hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, or substituted or unsubstituted C2 to C30 heterocyclyl.

[0091] m is an integer from 0 to 2.

[0092] The second compound for an organic photoelectric element is used together with the compound for an organic photoelectric element in a light emitting layer to increase charge mobility and stability, thereby improving light emitting efficiency and lifespan characteristics.

[0093] For example, Y in formula 2 1 and Y 2 It may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted pyridyl group.

[0094] In an embodiment, Y of Chemical Formula 21 and Y 2 The groups may independently be substituted or unsubstituted phenyl groups or substituted or unsubstituted biphenyl groups, but are not limited thereto.

[0095] For example, L in formula 2 1 and L 2 may independently be a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group. 4 To R 7 may independently be hydrogen, deuterium, or a substituted or unsubstituted C6 to C12 aryl group, and m may be 0 or 1.

[0096] In an embodiment, L of Chemical Formula 2 1 and L 2 may independently be a single bond, substituted or unsubstituted phenylene, R 4 To R 7 may independently be hydrogen, and m may be 0, but is not limited thereto.

[0097] For example, “substituted” of Chemical Formula 2 means that at least one hydrogen is replaced by deuterium, a C1 to C4 alkyl group, a C6 to C18 aryl group, or a C2 to C30 heteroaryl group.

[0098] In a specific embodiment, Chemical Formula 2 can be represented by Chemical Formula 2A.

[0099] [Chemical Formula 2A]

[0100]

[0101] In Chemical Formula 2A, Y 1 , Y 2 , L 1 , L 2 , R a and R 4 To R 7 Same as above.

[0102] For example, Chemical Formula 2 is one of the structures of Group II, and *-L 1 -Y 1 and -L 2 -Y 2 It may be one of the substituents of Group II.

[0103] [Group II]

[0104]

[0105] [Group III]

[0106]

[0107] In Group II and Group III, * is the connection point.

[0108] In an embodiment, Chemical Formula 2 is represented by Chemical Formula C-8 or Chemical Formula C-17 of Group II, and *-L 1 -Y 1 and *-L 2 -Y 2 Can be selected from Group III.

[0109] Specifically, Y in Chemical Formula 2 1 and Y 2 may independently be substituted or unsubstituted phenyl or substituted or unsubstituted biphenyl, and for example, *-L 1 -Y 1 and *-L 2 -Y 2 It may be selected from B-1, B-2 and B-3 of Group III, but is not limited thereto.

[0110] In a specific embodiment of the present invention, the first compound for an organic photoelectric element may be represented by Chemical Formula 1A or Chemical Formula 1B, and the second compound for an organic photoelectric element may be represented by Chemical Formula 2A.

[0111] Here, R in Chemical Formula 1A and Chemical Formula 1B 1 To R 3 may each be hydrogen, and Ar in Chemical Formula 1A 1 and Ar 2 may independently be substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, or substituted or unsubstituted terphenyl, provided that Ar 1 and Ar 2 are not both unsubstituted phenyl, and

[0112] Ar in Formula 1B 1 and Ar 2 The groups may independently be substituted or unsubstituted phenyl groups, substituted or unsubstituted biphenyl groups, or substituted or unsubstituted terphenyl groups.

[0113] In addition, Y in Chemical Formula 2A 1 and Y 2 may independently be substituted or unsubstituted phenyl or substituted or unsubstituted biphenyl, and L 1 and L 2 may independently be a single bond or a substituted or unsubstituted C6 to C12 arylene group, and R 4 To R 7 may each be hydrogen.

[0114] For example, the compound for an organic photoelectric element may be one of the compounds selected from Group 2, but is not limited thereto.

[0115] [Group 2]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122] The first compound for an organic photoelectric element and the second compound for an organic photoelectric element may be included in a weight ratio of 1:99 to 99:1. Within this range, the electron transport capability of the first compound for an organic photoelectric element and the hole transport capability of the second compound for an organic photoelectric element may be used to adjust the desired weight ratio to achieve bipolar characteristics, and thus improve efficiency and lifespan. Within this range, for example, they may be included in a weight ratio of about 10:90 to about 90:10, about 20:80 to about 80:20, such as about 20:80 to about 70:30, about 20:80 to about 60:40, and about 20:80 to about 50:50. For example, they may be included in a weight ratio of 20:80 to 40:60, such as a weight ratio of 30:70, 40:60, or 50:50, such as a weight ratio of 30:70.

[0123] In addition to the aforementioned first compound for an organic photoelectric element and the second compound for an organic photoelectric element, at least one compound may be included.

[0124] The aforementioned compound for an organic photoelectric element or the composition for an organic photoelectric element may be a composition further including a dopant.

[0125] The dopant may be, for example, a phosphorescent dopant, such as a red, green, or blue phosphorescent dopant, and may be, for example, a green or red phosphorescent dopant.

[0126] The dopant is a material mixed in a small amount with a compound for an organic photoelectric element or a composition for an organic photoelectric element to cause light emission, and may generally be a material such as a metal complex, which emits light by multiple excitations to a triplet state or a multiplet state. The dopant may be, for example, an inorganic, organic, or organic-inorganic compound, and one or more types of dopants may be used.

[0127] An embodiment of the dopant may be a phosphorescent dopant, and an embodiment of the phosphorescent dopant may be an organic metal compound including Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or a combination thereof. The phosphorescent dopant may be, for example, a compound represented by the chemical formula Z, but is not limited thereto.

[0128] [Chemical formula Z]

[0129] L 3 MX

[0130] In the chemical formula Z, M is a metal and L 3 is the same as or different from X and is a ligand that forms a coordination compound with M.

[0131] M can be, for example, Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or a combination thereof, and L 3 and X may be, for example, a bidentate ligand.

[0132] The aforementioned compound for an organic photoelectric element or the composition for an organic photoelectric element may be formed by a dry film forming method such as chemical vapor deposition (CVD).

[0133] Hereinafter, an organic photoelectric element including the aforementioned compound for an organic photoelectric element or the composition for an organic photoelectric element is described.

[0134] Without particular limitation, the organic photoelectric element may be any element that converts electrical energy into light energy and vice versa, and may be, for example, an organic optoelectronic element, an organic light emitting diode, an organic solar cell, and an organic photosensitive drum.

[0135] Herein, an organic light emitting diode as one embodiment of an organic photoelectric element is described with reference to the accompanying drawings.

[0136] Figure 1 and Figure 2 is a cross-sectional view showing an organic light emitting diode according to an embodiment.

[0137] refer to Figure 1 , the organic light emitting diode 100 according to the embodiment includes an anode 120 and a cathode 110 facing each other and an organic layer 105 disposed between the anode 120 and the cathode 110 .

[0138] The anode 120 may be made of a conductor having a large work function to facilitate hole injection, and may be, for example, a metal, a metal oxide, and / or a conductive polymer. For example, the anode 120 may be: a metal or an alloy thereof, such as nickel, platinum, vanadium, chromium, copper, zinc, gold, etc.; a metal oxide, such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc.; a metal and an oxide, such as ZnO and Al or SnO 2 and Sb; conductive polymers such as poly(3-methylthiophene), poly(3,4-(ethylene-1,2-dioxy)thiophene) (PEDOT), polypyrrole and polyaniline, but not limited thereto.

[0139] The cathode 110 may be made of a conductor having a small work function to facilitate electron injection, and may be, for example, a metal, a metal oxide, and / or a conductive polymer. For example, the cathode 110 may be: a metal or an alloy thereof, such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum silver, tin, lead, cesium, barium, etc.; a multilayer structure material, such as LiF / Al, LiO 2 / Al, LiF / Ca, LiF / Al and BaF 2 / Ca, but not limited thereto.

[0140] The organic layer 105 may include the aforementioned compound for an organic photoelectric element or a composition for an organic photoelectric element.

[0141] The organic layer 105 may include a light emitting layer 130 , which may include the aforementioned compound for an organic photoelectric element or a composition for an organic photoelectric element.

[0142] The composition for an organic photoelectric element further comprising a dopant may be, for example, a green or red light emitting composition.

[0143] For example, the light emitting layer 130 may include the aforementioned first compound for an organic photoelectric element and a second compound for an organic photoelectric element as a phosphorescent host.

[0144] The organic layer may further include an auxiliary layer in addition to the light emitting layer.

[0145] The auxiliary layer may be, for example, a hole auxiliary layer 140 .

[0146] refer to Figure 2 In addition to the light emitting layer 130 , the organic light emitting diode 200 further includes a hole auxiliary layer 140 . The hole auxiliary layer 140 further increases hole injection and / or hole mobility and blocks electrons between the anode 120 and the light emitting layer 130 .

[0147] For example, the hole auxiliary layer 140 may include at least one of group D compounds.

[0148] Specifically, the hole auxiliary layer 140 may include a hole transport layer between the anode 120 and the light emitting layer 130 and a hole transport auxiliary layer between the light emitting layer 130 and the hole transport layer, and at least one of the group D compounds may be included in the hole transport auxiliary layer.

[0149] [Group D]

[0150]

[0151]

[0152]

[0153] In the hole transport auxiliary layer, in addition to the compound, known compounds disclosed in US 5061569 A, JP 1993-009471 A, WO 1995-009147 A1, JP 1995-126615 A, JP 1998-095973 A, etc. and compounds similar thereto can be used.

[0154] In an embodiment, Figure 1 or Figure 2 In the embodiment, the organic light emitting diode may further include an electron transport layer, an electron injection layer or a hole injection layer as the organic layer 105 .

[0155] The organic light emitting diodes 100 and 200 may be manufactured by forming an anode or a cathode on a substrate, forming an organic layer using a dry film forming method such as vacuum deposition (evaporation), sputtering, plasma plating, and ion plating, and forming a cathode or an anode thereon.

[0156] The organic light emitting diode may be applied to an organic light emitting display device.

[0157] [Modes for Carrying Out the Invention]

[0158] Hereinafter, the embodiments are described in more detail with reference to Examples. However, these Examples are exemplary, and the scope of the present invention is not limited thereto.

[0159] Hereinafter, raw materials and reactants used in Examples and Synthesis Examples were purchased from Sigma-Aldrich Co. Ltd., TCI Inc., Tokyo chemical industry or P&H tech unless specifically commented or synthesized by a known method.

[0160] (Preparation of compounds for organic optoelectronic devices)

[0161] The compound for an organic photoelectric element as a specific embodiment of the present invention was synthesized by the following steps.

[0162] (Preparation of the first compound for organic photoelectric element)

[0163] (Preparation of the First Compound)

[0164] Synthesis Example 1: Synthesis of Compound A-2

[0165] [Reaction Scheme 1]

[0166]

[0167] 1) Synthesis of intermediate A-2-1

[0168] 30g (87.2mmol) 2-chloro-4-phenyl-6-(4-biphenylyl)-1,3,5-triazine, 100mL tetrahydrofuran, 100mL toluene and 100mL distilled water are added together in a 500mL round-bottomed flask, and 0.9 equivalent (4-chlorophenyl) boronic acid, 0.03 equivalent of tetrakis triphenylphosphine palladium and 2 equivalents of potassium carbonate are added thereto, and then heated to reflux under a nitrogen atmosphere. After 6 hours, the reaction solution is cooled, the water layer is removed therefrom, and then the organic layer is dried under reduced pressure. The solid obtained is washed with water and hexane, and recrystallized with 200mL toluene to obtain 24g (yield: 65%) of intermediate A-2-1.

[0169] 2) Synthesis of intermediate A-2-2

[0170] In a 1L round-bottom flask, 3-bromocarbazole (35g, 142mmol) is dissolved in tetrahydrofuran 0.5L, and phenylboric acid (17.3g, 142mmol) and tetrakis triphenylphosphine palladium (8.2g, 7.1mmol) are added thereto and then stirred. Subsequently, potassium carbonate (49.1g, 356mmol) saturated in water is added thereto, and then heated and refluxed at 80°C for 12 hours. When the reaction is complete, water is added to the reaction solution, then extracted with dichloromethane, treated with anhydrous magnesium sulfite to remove moisture, and then filtered and concentrated under reduced pressure. The residue obtained is separated and purified by column chromatography to obtain 22.0g (yield: 64%) of intermediate A-2-2.

[0171] 3) Synthesis of Compound A-2

[0172] Intermediate A-2-1 (24 g, 57.2 mmol), 1 equivalent of intermediate A-2-2, 1.5 equivalents of sodium tert-butoxide (NaOtBu), 0.04 equivalents of Pd 2 (dba) 3and 1.5 equivalents of tri-tert-butylphosphine (P(tBu) 3 ) (50% in toluene) was added to xylene (300 mL), and then heated to reflux for 12 hours under a nitrogen stream. After removing xylene, the solid crystallized by adding 200 mL of methanol to the obtained mixture was filtered, dissolved in monochlorobenzene (MCB), and filtered through silica gel / diatomaceous earth, and an appropriate amount of organic solvent was concentrated to obtain 22.2 g (yield: 62%) of compound A-2.

[0173] Synthesis Example 2: Synthesis of Compound A-25

[0174] [Reaction Scheme 2]

[0175]

[0176] 1) Synthesis of intermediate A-25-1

[0177] By using 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (30 g, 77.3 mmol), 21.4 g (yield: 66%) of Intermediate A-25-1 was obtained in the same manner as in step 1) of Synthesis Example 1.

[0178] 2) Synthesis of Compound A-25

[0179] By using Intermediate A-25-1 (21.4 g, 51 mmol), 19.8 g (yield: 62%) of Compound A-25 was obtained in the same manner as in Step 3) of Synthesis Example 1.

[0180] Synthesis Example 3: Synthesis of Compound A-3

[0181] [Reaction Scheme 3]

[0182]

[0183] Compound A-3 was synthesized in the same manner as in step 3) of Synthesis Example 1 by using intermediate A-3-1 (CAS No. 1910061-39-0).

[0184] Synthesis Example 4: Synthesis of Compound A-15

[0185] [Reaction Scheme 4]

[0186]

[0187] Compound A-15 was synthesized in the same manner as in step 3) of Synthesis Example 1 by using intermediate A-15-1 (CAS No. 2305965-85-7).

[0188] Comparative Synthesis Example 1: Synthesis of Compound R-1

[0189] [Reaction Scheme 5]

[0190]

[0191] Compound R-1 was synthesized in the same manner as in Synthesis Example 1 using 2-chloro-4,6-diphenyl-1,3,5-triazine.

[0192] Comparative Synthesis Example 2: Synthesis of Compound R-2

[0193] [Reaction Scheme 6]

[0194]

[0195] Compound R-2 was synthesized in the same manner as in Synthesis Example 1 by using (3-chlorophenyl)boronic acid instead of (4-chlorophenyl)boronic acid.

[0196] Comparative Synthesis Example 3: Synthesis of Compound R-3

[0197] [Reaction Scheme 7]

[0198]

[0199] Compound R-3 was synthesized in the same manner as in Synthesis Example 1 by using (4-biphenyl)boronic acid instead of phenylboronic acid in step 2) of Synthesis Example 1.

[0200] Comparative Synthesis Example 4: Synthesis of Compound R-4

[0201] [Reaction Scheme 8]

[0202]

[0203] 1) Synthesis of intermediate R-4-1

[0204] 1 equivalent of intermediate A-2-2, 1.2 equivalents of 4-chloro-1-bromobenzene, 2 equivalents of sodium tert-butoxide and 0.05 equivalents of Pd 2 (dba) 3 Suspended in xylene at 0.2M, and 2 equivalents of tri-tert-butylphosphine were added thereto, and then refluxed and stirred for 18 hours. Subsequently, methanol and 1.5 times of solvent were added thereto, and then stirred, and the solid obtained therefrom was filtered and washed with 300mL of water. The solid was recrystallized with monochlorobenzene to obtain intermediate R-4-1 (yield: 85%).

[0205] 2) Synthesis of intermediate R-4-2

[0206] In a 500mL round-bottomed flask, 16.42g (46.4mmol) of intermediate R-4-1 is added to 200mL toluene, and under nitrogen, 0.05 equivalent of dichlorodiphenylphosphinoferrocene palladium, 1.2 equivalents of bis-pinacol than diboron and 2 equivalents of potassium acetate are added thereto, and then heated and refluxed for 18 hours. The reaction solution is cooled, then dripped into 1L water to capture solid. The solid is dissolved in boiling toluene to process activated carbon and filtered through silica gel, and the filtrate from it is concentrated. The concentrated solid is stirred and filtered with a small amount of hexane, to obtain intermediate R-4-2 (yield: 85%).

[0207] 3) Synthesis of intermediate R-4-3

[0208] In a 500mL round-bottomed flask, 22.6g (100mmol) 2,4-dichloro-6-phenyltriazine is added to 100mL tetrahydrofuran, 100mL toluene and 100mL distilled water, and 0.9 equivalent of dibenzofuran-3-boric acid, 0.03 equivalent of tetrakis triphenylphosphine palladium and 2 equivalents of potassium carbonate are added thereto, and then heated and refluxed under nitrogen. After 6 hours, the reaction solution is cooled, the water layer is removed therefrom, and then the organic layer is dried under reduced pressure. The solid obtained is washed with water and hexane, and recrystallized in 200mL toluene, to obtain the intermediate R-4-3 of 26.0g (yield: 60%).

[0209] 4) Synthesis of Compound R-4

[0210] In a 500mL round-bottomed flask, 1 equivalent of intermediate R-4-2 is added in the distilled water of 80mL tetrahydrofuran (THF) and 40mL, and to it, add 1 equivalent of intermediate R-4-3, 0.03 equivalent of tetrakis triphenylphosphine palladium and 2 equivalents of potassium carbonate, and then heat and reflux under a nitrogen atmosphere.After 18 hours, cool reaction solution, and filter wherein precipitated solid and use 500mL water washing.With 500mL monochlorobenzene, solid is carried out recrystallization to obtain (productive rate: 70%) compound R-4.

[0211] Comparative Synthesis Example 5: Synthesis of Compound R-5

[0212] [Reaction Scheme 9]

[0213]

[0214] Using 9-(4-(4,4,5,5-tetramethyl-1,3,2-dioxolyl)-phenyl)-carbazole (cas:785051-54-9) and intermediate R-1-1, compound R-5 was obtained by the same synthesis method as in step 4) of Comparative Synthesis Example 4 (yield: 70%).

[0215] Reference Synthesis Example: Synthesis of Compound R-6

[0216] [Reaction Scheme 10]

[0217]

[0218] 1) Synthesis of compound R-6-1

[0219] Intermediate R-6-1 was obtained by the same synthesis method as in step 2) of Synthesis Example 1 by using 3,6-dibromo-9H-carbazole (yield: 75%).

[0220] 2) Synthesis of Comparative Compound R-6

[0221] By using intermediate R-6-1, compound R-6 was obtained by the same synthesis method as in step 3) of Synthesis Example 1 (yield: 70%).

[0222] (Preparation of the Second Compound for Organic Photoelectric Element)

[0223] Synthesis Example 5: Synthesis of Compound B-99

[0224] Compound B-99 was synthesized in the same manner as known in US2017-0317293A1.

[0225] (Manufacturing of organic light-emitting diodes)

[0226] Example 1

[0227] The coating will have a thickness of The glass substrate of ITO (indium tin oxide) was washed with distilled water and ultrasonic waves. After washing with distilled water, the glass substrate was ultrasonically washed with a solvent (such as isopropyl alcohol, acetone, methanol, etc.) and dried, and then moved to a plasma cleaner, cleaned with oxygen plasma for 10 minutes, and moved to a vacuum depositor. The ITO transparent electrode thus obtained was used as an anode, and compound A was vacuum-deposited on the ITO substrate to form A hole injection layer is formed, and compound B is deposited on the injection layer to thick, and then compound C is deposited as On the hole transport layer, a 2-nitrogen-doped polyvinyl chloride (PhGD) was formed by using the compound A-2 obtained in Synthesis Example 1 as a host and doping 15 wt % of PhGD as a dopant by vacuum deposition. Subsequently, on the light-emitting layer, a thin film of compound D and Liq was formed by simultaneously vacuum depositing the compound D and Liq at a ratio of 1:1. A thick electron transport layer is formed, and Liq and Al are vacuum deposited sequentially on the electron transport layer. Thick and harmonious thick, thereby manufacturing an organic light emitting diode.

[0228] The organic light emitting diode has five organic thin layers, and specifically has the following structure.

[0229] ITO / Compound A / Compound B / Compound C / EML[Compound A-2:PhGD (15wt%)] / Compound D:Liq / Liq / Al

[0230] Compound A: N4, N4'-diphenyl-N4, N4'-bis(9-phenyl-9H-carbazole-3-yl)biphenyl-4, 4'-diamine

[0231] Compound B: 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile (HAT-CN)

[0232] Compound C: N-(biphenyl-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine

[0233] Compound D: 8-(4-(4,6-di(naphthalen-2-yl)-1,3,5-triazin-2-yl)phenyl)quinoline

[0234]

[0235] Examples 2 to 5, Comparative Examples 1 to 5 and Reference Examples

[0236] As shown in Tables 1-4, each diode of Examples 2 to 5, Comparative Examples 1 to 5 and Reference Example was manufactured according to the same method as Example 1 except that the host, the ratio of the host and the dopant ratio were changed.

[0237] Evaluation: Driving voltage improvement and luminous efficiency and life extension effects

[0238] The driving voltage, luminous efficiency and lifespan characteristics of the organic light emitting diodes of Examples 1 to 5, Comparative Examples 1 to 5 and Reference Example were evaluated. The specific measurement method is as follows, and the results are shown in Tables 1 to 4.

[0239] (1) Measurement of current density changes according to voltage changes

[0240] The obtained organic light emitting diode was measured with respect to a current value flowing in a unit cell while increasing a voltage from 0 V to 10 V using a current-voltage meter (Keithley 2400), and the measured current value was divided by an area to provide a result.

[0241] (2) Measurement of brightness changes based on voltage changes

[0242] While increasing the voltage of the organic light emitting diode from 0 V to 10 V, the luminance was measured using a luminance meter (Minolta Cs-1000A).

[0243] (3) Measurement of luminous efficiency

[0244] By using the luminance and current density from items (1) and (2), the 2 ) under current efficiency (cd / A).

[0245] (4) Lifespan measurement

[0246] By 24000cd / m 2 Initial brightness (cd / m 2 ) emits light and measures the decrease in luminance over time to obtain the time when the luminance drops to 90% of the initial luminance as the T90 lifetime to measure the organic light emitting diodes of Examples 1 to 5, Comparative Examples 1 to 5 and the reference example relative to the T90 lifetime.

[0247] (5) Measurement of driving voltage

[0248] The ampere-voltmeter (Keithley 2400) was used to measure the 2 The driving voltage of each diode is measured.

[0249] (6) Calculation of T90 life ratio (%)

[0250] The relative T90(h) comparison values ​​of the single host or the mixed host of the examples using the same second host (the first compound for an organic photoelectric element as the first host) and the mixed host of the comparative example (the compound of the comparative example or reference example as the first host) were calculated.

[0251] T90 lifetime ratio (%) = {[T90 (h) of Example (applying the first compound for an organic photoelectric element as a single host or a mixed host) / [T90 (h) of Comparative Example (applying the compound of Comparative Example or Reference Example as a single host or a mixed host)]} × 100

[0252] (7) Calculation of driving voltage ratio (%)

[0253] A relative comparison value of a single host or a mixed host obtained by applying the same second host of Example (the first compound for an organic photoelectric element as the first host) and the mixed host of Comparative Example (the compound of Comparative Example or Reference Example as the first host) was calculated.

[0254] Driving voltage ratio (%) = {[driving voltage (V) of the embodiment (applying the first compound for an organic photoelectric element as a single host or a mixed host)] / [driving voltage (V) of the comparative example (the compound of the comparative example or reference example as a single host or a mixed host)]} × 100

[0255] (8) Calculation of luminous efficiency ratio

[0256] Relative comparison values ​​of a single host or a mixed host obtained by applying the same second host of Example (applying the first compound for an organic photoelectric element as the first host) and a mixed host of Comparative Example (compounds of Comparative Example or Reference Example as the first host) were calculated.

[0257] Luminous efficiency ratio (%) = {[luminous efficiency (cd / A) of the embodiment (applying the first compound for an organic photoelectric element as a single host or a mixed host)] / [luminous efficiency (cd / A) of the comparative example (the compound of the comparative example or the reference example as a single host or a mixed host)]} × 100

[0258] [Table 1]

[0259] Single Entity Dopant ratio (wt%) Driving voltage(V) Example 1 A-2 15 3.58 Comparative Example 1 R-2 15 3.85 Comparative Example 2 R-1 15 3.73 Reference example R-6 15 3.81

[0260] [Table 2]

[0261]

[0262] [Table 3]

[0263]

[0264] [Table 4]

[0265]

[0266] Referring to Tables 1 to 4, the compound for an organic photoelectric element according to the present invention exhibits reduced driving voltage and improved lifespan and luminous efficiency, compared with the compound for an organic photoelectric element according to the comparative example.

[0267] While the invention has been described in connection with what is presently considered to be practical embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but on the contrary, the invention is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. A compound for an organic photoelectric element, represented by Chemical Formula 1: [Chemical formula 1] in, In Chemical Formula 1, R 1 To R 3 are independently hydrogen, deuterium, cyano, or substituted or unsubstituted C1 to C10 alkyl, Ar 1 and Ar 2 are independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl or substituted or unsubstituted terphenyl, n is an integer of 0 or 1, and does not include Ar 1 and Ar 2 is a substituted or unsubstituted phenyl group, and Herein, "substituted" refers to replacement of at least one hydrogen of the substituted group by deuterium, C1 to C5 alkyl or cyano.

2. The compound according to claim 1, wherein Ar 1 and Ar 2 A group independently selected from Group I: [Group I] Where, in group I, * is the connection point.

3. The compound according to claim 1, wherein the compound is one of the compounds of the following Group 1: [Group 1] 4. A composition for an organic optoelectronic element, comprising A first compound for an organic photoelectric element; and A second compound for an organic optoelectronic element, in, The first compound for an organic photoelectric element is represented by Chemical Formula 1 in claim 1, and The second compound for an organic photoelectric element is represented by Chemical Formula 2A: [Chemical Formula 2A] Wherein, in Chemical Formula 2A, Y 1 and Y 2 are independently substituted or unsubstituted phenyl or substituted or unsubstituted biphenyl, L 1 and L 2 are independently a single bond, or a substituted or unsubstituted phenylene group or a substituted or unsubstituted biphenylene group, R 4 To R 7 are independently hydrogen, deuterium or substituted or unsubstituted C6 to C12 aryl, and Here, "substituted" refers to replacement of at least one hydrogen of the substituted group by deuterium or C1 to C4 alkyl.

5. The composition according to claim 4, wherein *-L 1 -Y 1 and *-L 2 -Y 2 is one of the substituents of Group III: [Group III] Among them, in Group II and Group III, * is the connection point.

6. The composition according to claim 5, wherein *-L 1 -Y 1 and *-L 2 -Y 2 Independently selected from B-1, B-2 and B-3 of Group III.

7. An organic photoelectric element, comprising The anode and cathode are opposite to each other. at least one organic layer between the anode and the cathode, The organic layer comprises the compound for an organic photoelectric element according to any one of claims 1 to 3; or A composition for an organic optoelectronic device according to any one of claims 4 to 6.

8. The organic photoelectric element according to claim 7, wherein The organic layer includes a light-emitting layer, and The light-emitting layer includes the compound for an organic photoelectric element or the composition for an organic photoelectric element. 9 . A display device comprising the organic photoelectric element according to claim 7 .

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