Compounds, light-emitting materials, and organic light-emitting devices

Abstract

This compound represented by the following general formula has excellent light emitting properties. Ar1 represents a benzene ring, a naphthalene ring, a phenanthrene ring, or the like, D represents a 5H-indolo[3,2,1-de]phenazin-5-yl group or the like, A represents a cyano group, a phenyl group, a pyrimidyl group, a triazyl group, or the like, m represents 1 or 2, n represents 0-2, and R1-R4 each represent H, an aryl group, a cyano group, or the like.

Description

[Technical Field]

[0001] This invention relates to compounds having good luminescence properties. The invention also relates to luminescent materials and organic light-emitting devices using these compounds. [Background technology]

[0002] Organic light-emitting devices (OLEDs) are light-emitting devices that use organic materials, can be manufactured by coating, and do not use rare elements, which has attracted attention in recent years. Among them, organic electroluminescent devices (OLEDs) have the advantage of being lightweight and flexible because they emit light themselves and do not require a backlight. They also have the characteristics of fast response and high visibility, and are expected to be the next generation of light sources. For this reason, research on the development of materials useful for organic light-emitting devices, including organic electroluminescent devices, is being actively pursued. Research on light-emitting materials in particular is being actively conducted (for example, Non-Patent Document 1). [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] Chem. Soc. Rev., 2017, 46, 915 [Overview of the project] [Problems that the invention aims to solve]

[0004] On the other hand, there is still room for improvement in the luminescence characteristics of organic light-emitting devices, and further improvements in luminescence characteristics are needed. Therefore, the present inventors diligently pursued research with the aim of developing novel compounds that contribute to improving the luminescence characteristics of organic light-emitting devices. [Means for solving the problem]

[0005] As a result of intensive studies, the present inventors have found that a compound having a group with a structure characteristic of a specific skeleton is a compound useful for a light-emitting device. The present invention has been proposed based on such findings and has the following configuration.

[0006] [1] A compound represented by the following general formula (1). General formula (1) [Chemical formula] [In general formula (1), Ar 1 represents a cyclic structure and represents a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring. D represents a group represented by the following general formula (2). A represents one group selected from the group consisting of a cyano group, a phenyl group, a pyrimidyl group, a triazyl group, and an alkyl group or a group formed by combining two or more thereof (excluding a substituted alkyl group). m is 1 or 2, and n is 0, 1, or 2. When m is 2, the two Ds may be the same or different. When n is 2, the two As may be the same or different. R 1 ~R 4 each independently represents a hydrogen atom, a deuterium atom, or one group selected from the group consisting of an alkyl group, an aryl group, a heteroaryl group, and a cyano group or a group formed by combining two or more thereof. R 1 and R 2 , R 3 and R 4 may combine with each other to form a cyclic structure selected from the group consisting of a benzene ring, a naphthalene ring, and a pyridine ring, and the formed cyclic structure may be substituted with one group selected from the group consisting of an alkyl group, an aryl group, a heteroaryl group, and a cyano group or a group formed by combining two or more thereof.] General formula (2) [Chemical formula] [In general formula (2), R 5 ~R 15 each independently represents a hydrogen atom, a deuterium atom, or a substituent. R 5 and R6 , R 6 and R 7 , R 8 and R 9 , R 9 and R 10 , R 10 and R 11 , R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 These atoms may be bonded to each other to form a cyclic structure. X represents a single bond, an oxygen atom, or a sulfur atom. * indicates a bond position. [2] The compound described in [1], represented by the following general formula (3). General formula (3) [ka] [In general formula (3), Ar 1 The 'D' represents a cyclic structure, specifically a benzene ring, naphthalene ring, anthracene ring, or phenanthrene ring. D represents the group represented by the general formula (2) above. A represents one or more groups selected from the group consisting of cyano, phenyl, pyrimidyl, triazyl, and alkyl groups (excluding substituted alkyl groups). m is 1 or 2, and n is 0, 1, or 2. When m is 2, the two D's may be the same or different. When n is 2, the two A's may be the same or different. Ar 2 Ar 3 Each of these may independently form a cyclic structure selected from the group consisting of a benzene ring, a naphthalene ring, and a pyridine ring, and the formed cyclic structure may be substituted with one or more groups selected from the group consisting of alkyl groups, aryl groups, heteroaryl groups, and cyano groups. [3] The compound described in [1] having one of the following skeletons. [ka] [Each of the above skeletons may have substituents within the range of general formula (1), but no further rings are fused to the skeleton.] [4] A compound described in [1], represented by any of the following general formulas (4a) to (4f). [ka] [In general formulas (4a) to (4f), R 21 ~R 28 , R 41 ~R 44 , R 51 , R 52 , R 61 ~R 68 , R 81 ~R 84 , R 101 ~R 104 , R 111 ~R 114 , R 119 , R 120 Each of these independently represents a hydrogen atom, a deuterium atom, D, or A. However, R 21 ~R 28 One or two of them are D and 0 to 2 are A, R 41 ~R 44 , R 51 and R 52 One or two of them are D and 0 to 2 are A, R 61 ~R 68 One or two of them are D and 0 to 2 are A, R 81 ~R 84 One or two of them are D and 0 to 2 are A, R 101 ~R 104 One or two of them are D and 0 to 2 are A, R 111 ~R 114 , R 119 and R 120 One or two of them are D, and zero to two are A. 29 ~R 36 , R 45 ~R 50 , R 69 ~R 72 , R 85 ~R 92 , R 105 ~R 110 , R 115 ~R 118Each of these independently represents a hydrogen atom, a deuterium atom, or one or more groups selected from the group consisting of alkyl groups, aryl groups, and cyano groups. [5] A compound described in any one of [1] to [4], wherein n is 0. A luminescent material comprising any one of the compounds described in [6] [1] to [5]. [7] A membrane containing any one of the compounds described in [1] to [5]. [8] An organic semiconductor device containing one of the compounds described in any one of [1] to [5]. [9] An organic light-emitting element containing one of the compounds described in [1] to [5].

[10] The organic light-emitting element according to [9], wherein the element has a layer containing the compound, and the layer also contains a host material.

[11] The organic light-emitting element according to

[10] , wherein the layer containing the compound also contains a delayed fluorescence material in addition to the host material, and the lowest excitation singlet energy of the delayed fluorescence material is lower than that of the host material and higher than that of the compound.

[12] The organic light-emitting element according to [9], wherein the element has a layer containing the compound, and the light-emitting material also includes a layer having a structure different from that of the compound.

[13] The organic light-emitting element according to any one of [9] to

[11] , wherein the material contained in the element has the greatest amount of light emitted from the compound.

[14] The organic light-emitting device according to

[12] , wherein the amount of light emitted from the light-emitting material is greater than the amount of light emitted from the compound.

[15] An organic light-emitting device according to any one of [9] to

[14] , which emits delayed fluorescence. [Effects of the Invention]

[0007] The compounds of the present invention are useful for light-emitting devices. The compounds of the present invention can be used as light-emitting materials, and organic light-emitting devices can be manufactured using the compounds of the present invention. Organic light-emitting devices using the compounds of the present invention exhibit at least one excellent characteristic, such as luminous efficiency (especially at high concentrations), device durability, and improved color purity. [Brief explanation of the drawing]

[0008] [Figure 1] This is a schematic cross-sectional view showing an example of the layer structure of an organic electroluminescent element. [Modes for carrying out the invention]

[0009] The contents of the present invention will be described in detail below. The description of the constituent elements described below may be based on representative embodiments and specific examples of the present invention, but the present invention is not limited to such embodiments and specific examples. In this specification, numerical ranges represented by "~" mean a range that includes the numbers written before and after "~" as the lower limit and upper limit. Also, some or all of the hydrogen atoms present in the molecule of the compound used in the present invention are deuterium atoms ( 2 It can be substituted with H (deuterium D). In the chemical structural formulas herein, hydrogen atoms are either represented as H or omitted. For example, when the representation of an atom bonded to a carbon atom in the ring skeleton of a benzene ring is omitted, it is assumed that H is bonded to the carbon atom in the omitted portion. In this specification, the term "substituent" means an atom or group of atoms other than hydrogen and deuterium atoms. On the other hand, the term "substituted or unsubstituted" means that the hydrogen atom may be substituted with a deuterium atom or a substituent.

[0010] [Compounds represented by general formula (1)] The compound of the present invention is a compound represented by the following general formula (1).

[0011] [ka]

[0012] In general formula (1), Ar 1 The symbol represents a cyclic structure, specifically a benzene ring, naphthalene ring, anthracene ring, or phenanthrene ring. For example, Ar 1When Ar represents a benzene ring, it becomes a quinoxaline structure in which the benzene ring is fused to a pyrazine ring. 1 When represents a naphthalene ring, the pyrazine ring may have either a 1,2-naphtho ring or a 2,3-naphtho ring condensed to it. When a 1,2-naphtho ring is condensed to the pyrazine ring, the carbon atoms at positions 1 and 2 of the naphthalene ring are shared with the carbon atoms at positions 2 and 3 that make up the pyrazine ring, respectively. 1 When represents an anthracene ring, a 2,3-anthracene ring is fused to the pyrazine ring. 1 When represents a phenanthrene ring, the pyrazine ring may be fused with any of the following: a 1,2-phenanthrene ring, a 2,3-phenanthrene ring, a 3,4-phenanthrene ring, or a 9,10-phenanthrene ring. In a preferred embodiment of the present invention, a benzene ring, a 2,3-naphtho ring, or a 9,10-phenanthrene ring is fused to the pyrazine ring. In a more preferred embodiment of the present invention, a 2,3-naphtho ring or a 9,10-phenanthrene ring is fused to the pyrazine ring. For example, a 2,3-naphtho ring or a 9,10-phenanthrene ring may be fused.

[0013] Ar 1 The cyclic structure represented by has m D atoms and n A atoms bonded as substituents to the ring skeleton. 1 When represents a naphthalene ring, an anthracene ring, or a phenanthrene ring, D and A may be bonded to any of the benzene rings constituting these rings. Alternatively, m D and n A may be bonded to only one benzene ring, while neither D nor A may be bonded to the other benzene rings. Or, some of the m D and n A may be bonded to one benzene ring, and the remainder to another benzene ring. In one preferred embodiment of the present invention, n is 0, and m D are bonded to only one benzene ring. In another preferred embodiment of the present invention, n is 0, and some of the m D are bonded to one benzene ring, and the remainder to another benzene ring. 1When represents a naphthalene ring, anthracene ring, or phenanthrene ring, in a preferred embodiment of the present invention, neither D nor A is bonded to the benzene ring directly fused to the pyrazine ring, and only the remaining benzene rings (i.e., benzene rings not directly fused to the pyrazine ring) are bonded with m D and n A. 1 When represents a naphthalene ring, anthracene ring, or phenanthrene ring, in a preferred embodiment of the present invention, n is 0, and no D is bonded to the benzene ring directly fused to the pyrazine ring, while m Ds are bonded only to the remaining benzene rings (i.e., benzene rings not directly fused to the pyrazine ring).

[0014] In general formula (1), m is 1 or 2, and n is 0, 1, or 2. When m is 2, the two Ds may be the same or different. Also, the two Ds may be bonded to the same benzene ring or to different benzene rings. When n is 2, the two As may be the same or different. Also, the two As may be bonded to the same benzene ring or to different benzene rings. In a preferred embodiment of the present invention, n is 0. For example, m is 1 and n is 0. For example, m is 2 and n is 0. Ar 1 When n represents a naphthalene ring, anthracene ring, or phenanthrene ring, and n is 1 or 2, in one aspect of the present invention, a benzene ring to which D is bonded is not bonded to A, and a benzene ring to which A is bonded is not bonded to D.

[0015] In general formula (1), D represents the group represented by the following general formula (2). General formula (2) [ka]

[0016] In general formula (2), X represents a single bond, an oxygen atom, or a sulfur atom. In one preferred embodiment of the present invention, X is a single bond. In one preferred embodiment of the present invention, X is an oxygen atom. X may be an oxygen atom or a sulfur atom. In general formula (2), * represents the bonding position. In general formula (2), R 5 ~R 15 each independently represents a hydrogen atom, a deuterium atom or a substituent. The substituent may be selected, for example, from among the substituent group A, or from among the substituent group B, or from among the substituent group C, or from among the substituent group D, or from among the substituent group E. In a preferred embodiment of the present invention, the substituent means one group selected from the group consisting of an alkyl group (for example, having 1 to 20 carbon atoms), an aryl group (for example, having 6 to 22 carbon atoms) and a cyano group, or a group formed by combining two or more thereof. For example, the substituent may be an aryl group which may be substituted with one group selected from the group consisting of a cyano group, or a group formed by combining two or more thereof selected from the group consisting of a cyano group and an alkyl group. When two or more of R 5 ~R 15 represent substituents, the two or more substituents may be the same or different. It is preferable that 6 to 11 of R 5 ~R 15 are hydrogen atoms or deuterium atoms, and for example, 8 to 11 may be hydrogen atoms or deuterium atoms. All of R 5 ~R 15 may all be hydrogen atoms or deuterium atoms. Alternatively, 8 to 10 may be hydrogen atoms or deuterium atoms. For example, 8 may be hydrogen atoms or deuterium atoms, 9 may be hydrogen atoms or deuterium atoms, and 10 may be hydrogen atoms or deuterium atoms. R 5 and R 6 、R 6 and R 7 、R 8 and R 9 、R 9 and R 10 、R 10 and R 11 、R 11 and R 12 、R 12 and R 13 、R 13 and R 14 、R 14 and R 15These elements may be bonded to each other to form a cyclic structure. The cyclic structure may be an aromatic ring, a heteroaromatic ring, an aliphatic hydrocarbon ring, or an aliphatic heterocycle, or a ring formed by the fusion of these elements. Preferably, it is an aromatic ring or a heteroaromatic ring. A benzene ring can be given as an aromatic ring. A heteroaromatic ring means an aromatic ring that contains heteroatoms as constituent atoms of the ring skeleton, and is preferably a 5- to 7-membered ring; for example, a 5-membered ring or a 6-membered ring can be used. In one embodiment of the present invention, a furan ring, a thiophene ring, or a pyrrole ring can be used as the heteroaromatic ring. In a preferred embodiment of the present invention, the cyclic structure is a furan ring of substituted or unsubstituted benzofuran, a thiophene ring of substituted or unsubstituted benzothiophene, or a pyrrole ring of substituted or unsubstituted indole. The benzofuran, benzothiophene, and indole referred to here may be unsubstituted, substituted with substituents selected from substituent group A, substituents selected from substituent group B, substituents selected from substituent group C, substituents selected from substituent group D, or substituents selected from substituent group E. It is preferable that a substituted or unsubstituted aryl group is bonded to the nitrogen atom constituting the pyrrole ring of indole, and examples of such substituents include those selected from any of substituent groups A to E. 5 and R 6 , R 6 and R 7 , R 8 and R 9 , R 9 and R 10 , R 10 and R 11 , R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15In this configuration, it is preferable that 0 to 2 pairs are bonded to each other to form a ring structure, and more preferably that 0 or 1 pair are bonded to each other to form a ring structure. 1 or 2 pairs may be bonded to each other to form a ring structure. Alternatively, only 1 pair may be bonded to each other to form a ring structure. Furthermore, it is possible that 0 pairs are bonded to each other to form a ring structure.

[0017] Specific examples of D that can be used in general formula (1) are shown below. D that can be used in general formula (1) may include any group containing the following structure. For example, it may be a phenyl group substituted with a group having the following structure, or a group in which a ring (e.g., a benzene ring) is fused to a benzene ring in the following structure. The D that can be used in the present invention is not limited by the following specific examples. In the following specific examples, the wavy lines indicate the bond position. [ka] [ka] [ka] [ka] [ka] [ka]

[0018] In general formula (1), A represents one or more groups selected from the group consisting of cyano groups, phenyl groups, pyrimidyl groups, triazyl groups, and alkyl groups (excluding substituted alkyl groups). That is, A is a cyano group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyrimidyl group, or a substituted or unsubstituted triazyl group, and the substituents of the phenyl group, pyrimidyl group, and triazyl group are one or more groups selected from the group consisting of cyano groups, phenyl groups, pyrimidyl groups, triazyl groups, and alkyl groups, and a benzene ring may be fused to the phenyl group and pyrimidyl group. In a preferred embodiment of the present invention, A is a cyano group or a phenyl group substituted with a cyano group. In one embodiment of the present invention, A is a substituted or unsubstituted pyrimidyl group or a substituted or unsubstituted triazyl group, preferably a pyrimidyl group substituted with a substituted or unsubstituted phenyl group, or a triazyl group substituted with a substituted or unsubstituted phenyl group. In one embodiment of the present invention, A is a phenyl group substituted with a substituted or unsubstituted pyrimidyl group, or a phenyl group substituted with a substituted or unsubstituted triazyl group.

[0019] Specific examples of A that can be used in general formula (1) are shown below. A that can be used in general formula (1) may include any group containing the following structure. For example, it may be a phenyl group substituted with a group having the following structure, or a group in which a ring (e.g., a benzene ring) is fused to a benzene ring in the following structure. The A that can be used in the present invention is not limited by the following specific examples. In the following specific examples, * indicates the bond position. Also, the methyl group is omitted. For example, A15 is a group having two 4-methylphenyl groups. [ka] [ka]

[0020] R 1 ~R4 Each of these independently represents a hydrogen atom, a deuterium atom, or one or more groups selected from the group consisting of alkyl groups, aryl groups, heteroaryl groups, and cyano groups. That is, R 1 ~R 4 Each is independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a cyano group, and the substituents of the alkyl group, aryl group, and heteroaryl group are one or more groups selected from the group consisting of alkyl groups, aryl groups, heteroaryl groups, and cyano groups. In one aspect of the present invention, the substituent is an alkyl group which may be substituted with an aryl group, or an aryl group which may be substituted with an alkyl group. In one aspect of the present invention, the substituent is a cyano group, or an aryl group which is substituted with a cyano group, or a heteroaryl group. 1 ~R 4 When two or more of these are substituents, those substituents may be the same or different. 1 ~R 4 All of them may be hydrogen atoms or deuterium atoms. In one preferred embodiment of the present invention, R 1 ~R 4 Each of these is independently a hydrogen atom, a deuterium atom, or an aryl group which may be substituted with an alkyl group or a cyano group, or a pyridyl group, preferably a hydrogen atom, a deuterium atom, or a phenyl group which may be substituted with an alkyl group or a cyano group, or a pyridyl group. For example, one may select a hydrogen atom, a deuterium atom, an alkylphenyl group, a cyanophenyl group, a phenyl group, or a pyridyl group, or for example, a hydrogen atom, a deuterium atom, an alkylphenyl group, or a phenyl group. R 1 and R 2 , R 3 and R 4These may bond to each other to form a cyclic structure selected from the group consisting of a benzene ring, a naphthalene ring, and a pyridine ring, and the formed cyclic structure may be substituted with one or more groups selected from the group consisting of an alkyl group, an aryl group, and a cyano group. In one aspect of the present invention, R 1 and R 2 , R 3 and R 4 One of these pairs combines with each other to form a benzene ring, a naphthalene ring, and a pyridine ring. In one aspect of the present invention, R 1 and R 2 , R 3 and R 4 Both of them bond to each other to form a benzene ring, a naphthalene ring, and a pyridine ring. At this time, R 1 and R 2 The ring formed by and R 3 and R 4 The rings formed by may be the same or different. In one aspect of the present invention, R 1 and R 2 , R 3 and R 4 None of these are bonded to each other to form a ring. In one aspect of the present invention, the formed cyclic structure is a benzene ring or a naphthalene ring. In one aspect of the present invention, the formed cyclic structure is a pyridine ring. The hydrogen atoms bonded to the benzene ring, naphthalene ring, and pyridine ring may be substituted with deuterium atoms or substituents, and the substituents here include one group or a combination of two or more groups selected from the group consisting of alkyl groups, aryl groups, heteroaryl groups, and cyano groups. In one aspect of the present invention, the substituent is an alkyl group which may be substituted with an aryl group, or an aryl group which may be substituted with an alkyl group. In one aspect of the present invention, the substituent is a cyano group or an aryl group which is substituted with a cyano group. The hydrogen atoms bonded to the benzene ring, naphthalene ring, and pyridine ring do not need to be substituted.

[0021] The following are examples of aryl groups that may be substituted with the alkyl groups mentioned above. However, the aryl groups that may be substituted with alkyl groups that can be used in the present invention are not limited to the following examples. In the following examples, * indicates the bond position. Also, the methyl group is omitted. For example, N4 is a 4-methylphenyl group. Among these, N5, N8, N10, and N11 are preferred. [ka]

[0022] R in general formula (1) 1 ~R 4 Of these, N5 and tert-butyl groups are more preferred, and N5 is particularly preferred. The compound represented by general formula (1) may also be the compound represented by general formula (3) below. General formula (3) [ka]

[0023] In general formula (3), Ar 1 The 'D' represents a cyclic structure, specifically a benzene ring, naphthalene ring, anthracene ring, or phenanthrene ring. D represents the group represented by the general formula (2) above. A represents one or more groups selected from the group consisting of cyano, phenyl, pyrimidyl, triazyl, and alkyl groups (excluding substituted alkyl groups). m is 1 or 2, and n is 0, 1, or 2. When m is 2, the two D's may be the same or different. When n is 2, the two A's may be the same or different. Ar 2 Ar 3 Each of these may independently form a cyclic structure selected from the group consisting of a benzene ring, a naphthalene ring, and a pyridine ring, and the formed cyclic structure may be substituted with one or more groups selected from the group consisting of alkyl groups, aryl groups, heteroaryl groups, and cyano groups. Ar in general formula (3)1 For details and preferred ranges of D, A, m, and n, refer to the corresponding description in the general formula (1) above. 2 Ar 3 For details and preferred ranges of the benzene ring, naphthalene ring, and pyridine ring represented by R in the general formula (1) above, see R 1 and R 2 , R 3 and R 4 You can refer to descriptions of benzene rings, naphthalene rings, and pyridine rings formed by the bonding of these elements together.

[0024] In one aspect of the present invention, D in general formula (3) is a substituted or unsubstituted 5H-indoro[3,2,1-de]phenazine-5-yl group, A is a cyano group, a phenyl group, a pyrimidyl group, a triazyl group, or a benzonitrile group, n is 0 or 1, and Ar 2 Ar 3 Each of these is independently a benzene ring, a naphthalene ring, a pyridine ring, or a benzene ring substituted with a cyano group.

[0025] Compounds represented by general formula (1) preferably have one of the following ring skeletons. At least one hydrogen atom in the following skeletons may be substituted with a deuterium atom or a substituent within the range of general formula (1). However, no other rings are fused. Since D is always present in general formula (1), only one D is listed in the following ring skeletons.

[0026] [ka]

[0027] In a preferred embodiment of the present invention, the compound represented by general formula (1) has a ring skeleton of any of the following ring skeleton group 1. [ka]

[0028] In a preferred embodiment of the present invention, the compound represented by general formula (1) has a ring skeleton of any of the following ring skeleton group 2. [ka]

[0029] In one preferred embodiment of ring skeleton group 1 and ring skeleton group 2, A is not present in the molecule. In one embodiment of the present invention, the aromatic ring condensed below the pyrazine ring in ring skeleton group 1 and ring skeleton group 2 is bonded to a hydrogen atom, a deuterium atom, an unsubstituted alkyl group, or an aryl group which may be substituted with an alkyl group. In one preferred embodiment of the present invention, the aromatic ring condensed below the pyrazine ring in ring skeleton group 1 and ring skeleton group 2 is bonded to a hydrogen atom, a deuterium atom, or an unsubstituted alkyl group.

[0030] The compound represented by general formula (1) may also be a compound represented by any of the following general formulas (4a) to (4f). [ka]

[0031] In general formulas (4a) to (4f), R 21 ~R 28 , R 41 ~R 44 , R 51 , R 52 , R 61 ~R 68 , R 81 ~R 84 , R 101 ~R 104 , R 111 ~R 114 , R 119 , R 120 Each of these independently represents a hydrogen atom, a deuterium atom, D, or A. However, R 21 ~R 28 One or two of them are D and 0 to 2 are A, R 41 ~R 44 , R 51 and R 52One or two of them are D and 0 to 2 are A, R 61 ~R 68 One or two of them are D and 0 to 2 are A, R 81 ~R 84 One or two of them are D and 0 to 2 are A, R 101 ~R 104 One or two of them are D and 0 to 2 are A, R 111 ~R 114 , R 119 and R 120 One or two of them are D, and zero to two are A. 29 ~R 36 , R 45 ~R 50 , R 69 ~R 72 , R 85 ~R 92 , R 105 ~R 110 , R 115 ~R 118 Each of these independently represents a hydrogen atom, a deuterium atom, or one or more groups selected from the group consisting of alkyl groups, aryl groups, and cyano groups. In general formulas (4a) to (4f), no further rings are fused to the described ring skeleton. For details and preferred ranges of general formulas (4a) to (4f), refer to the corresponding descriptions in general formula (1). In one aspect of the present invention, a compound represented by general formula (4a) is selected. In one aspect of the present invention, a compound represented by general formula (4b) is selected. In one aspect of the present invention, a compound represented by general formula (4c) is selected. In one aspect of the present invention, a compound represented by general formula (4d) is selected. In one aspect of the present invention, a compound represented by general formula (4e) is selected. In one aspect of the present invention, a compound represented by general formula (4f) is selected.

[0032] Tables 1 to 12 below illustrate specific examples of compounds represented by general formula (1). Tables 1 and 2 show specific examples of compounds represented by general formula (4a'), Tables 3 and 4 show specific examples of compounds represented by general formula (4b'), Tables 5 and 6 show specific examples of compounds represented by general formula (4c'), Tables 7 and 8 show specific examples of compounds represented by general formula (4d'), Tables 9 and 10 show specific examples of compounds represented by general formula (4e'), and Tables 11 and 12 show specific examples of compounds represented by general formula (4f'). However, the compounds represented by general formula (1) that can be used in the present invention should not be interpreted as being limited by these specific examples. [Table 1-1] [Table 1-2]

[0033] Table 2 below provides further examples of compounds represented by the general formula (4a') in table format. In Table 2, compounds are assigned to structures obtained by further substituting a part of the structure identified by the compound number. For example, in Table 2, compounds 101-150 (indicated as No. 101-150 in the table) are R compounds of compounds 1-50. 27 (Indicated as R27 in the table) Further R of compounds 1-50 22 This represents a compound substituted with the substituent corresponding to (indicated as R22 in the table). Compound 101 is the R of Compound 1. 27 R of compound 1 22 Compound 102 is a compound further substituted with D1, and compound 102 is R of compound 2. 27 R of compound 2 22 This is a compound further substituted with D2. In this manner, the structures of each compound listed in Table 2 and each compound listed in Tables 4, 6, 8, 10, and 12 are identified. In Tables 2, 4, 6, 8, 10, and 12, the structure of each numbered compound is identified individually and is disclosed one by one in this specification. Note that "t-Bu" in the tables represents a tert-butyl group.

[0034] Table 2

[0035] Table 3-1 Table 3-2

[0036] Table 4

[0037] Table 5-1 Table 5-2

[0038] Table 6

[0039] Table 7-1 Table 7-2

[0040] Table 8

[0041] Table 9-1 Table 9-2

[0042] [Table 10]

[0043] [Table 11-1] [Table 11-2]

[0044] [Table 12]

[0045] Furthermore, compounds 1d to 22600d are disclosed in which all hydrogen atoms in the molecules of compounds 1 to 22600 are replaced with deuterium atoms. If rotational isomers exist among the compounds exemplified above, both the mixture of rotational isomers and the separated rotational isomers are also disclosed herein.

[0046] In one aspect of the present invention, a compound having a line-symmetric structure is selected as the compound represented by general formula (1). In another aspect of the present invention, a compound having an asymmetric structure is selected as the compound represented by general formula (1). In one aspect of the present invention, compounds 1 to 3200 and 1d to 3200d are selected as compounds represented by general formula (1). In one aspect of the present invention, compounds 3201 to 5800 and 3201d to 5800d are selected as compounds represented by general formula (1). In one aspect of the present invention, compounds 5801 to 7800 and 5801d to 7800d are selected as compounds represented by general formula (1). In one aspect of the present invention, compounds 7801 to 11000 and 7801d to 11000d are selected as compounds represented by general formula (1). In one aspect of the present invention, compounds 11001 to 13600 and 11001d to 13600d are selected as compounds represented by general formula (1). In one aspect of the present invention, compounds 13601 to 16200 and 13601d to 16200d are selected as compounds represented by general formula (1). In one aspect of the present invention, compounds 16201 to 18200 and 16201d to 18200d are selected as compounds represented by general formula (1). In one aspect of the present invention, compounds 18201 to 22600 and 18201d to 22600d are selected as compounds represented by general formula (1).

[0047] Compounds represented by general formula (1) may not have acceptor groups bonded to the skeleton of general formula (1). Here, an acceptor group is a group with a positive Hammett σp value. Compounds represented by general formula (1) may not have groups with a Hammett σp value of 0.2 or greater.

[0048] The molecular weight of the compound represented by general formula (1) is preferably 1500 or less, more preferably 1200 or less, even more preferably 1000 or less, and even more preferably 900 or less, when the organic layer containing the compound represented by general formula (1) is intended to be used by forming a film by vapor deposition. The lower limit of the molecular weight is the molecular weight of the smallest compound in the group of compounds represented by general formula (1). Compounds represented by general formula (1) may be deposited as films by coating methods regardless of their molecular weight. Coating methods allow for the deposition of even relatively large molecular weight compounds. Compounds represented by general formula (1) have the advantage of being readily soluble in organic solvents. Therefore, coating methods are easily applied to compounds represented by general formula (1), and their purity can be easily increased through purification.

[0049] Applying the present invention, it is also conceivable to use a compound containing multiple structures represented by general formula (1) within its molecule as a light-emitting material. For example, it is conceivable to use a polymer obtained by polymerizing a polymerizable group that is already present in a structure represented by general formula (1) as a light-emitting material. Specifically, any of the structures represented by general formula (1) (for example, Ar 1 D, A, R 1 ~R 4 It is conceivable to prepare monomers containing polymerizable functional groups (either of the above) and polymerize them alone or copolymerize them with other monomers to obtain polymers having repeating units, which can then be used as luminescent materials. Alternatively, it is conceivable to obtain dimers or trimers by coupling compounds represented by general formula (1) and use them as luminescent materials.

[0050] Examples of polymers having repeating units that include a structure represented by general formula (1) include polymers that include a structure represented by either of the following two general formulas. [ka]

[0051] In the general formula above, Q represents a group containing the structure represented by general formula (1), and L 1 and L 2 The symbol represents a linking group. The number of carbon atoms in the linking group is preferably 0 to 20, more preferably 1 to 15, and even more preferably 2 to 10. The linking group is -X 11 -L 11It is preferable that the structure is represented by -. Here, X 11 L represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom. 11 The group represents a linking group, which is preferably a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, and more preferably a substituted or unsubstituted alkylene group or a substituted or unsubstituted phenylene group having 1 to 10 carbon atoms. R 201 , R 202 , R 203 and R 204 Each of these independently represents a substituent. Preferably, these are a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, or a halogen atom; more preferably, these are an unsubstituted alkyl group having 1 to 3 carbon atoms, an unsubstituted alkoxy group having 1 to 3 carbon atoms, a fluorine atom, or a chlorine atom; and even more preferably, these are an unsubstituted alkyl group having 1 to 3 carbon atoms or an unsubstituted alkoxy group having 1 to 3 carbon atoms. L 1 and L 2 The linking group represented by can be located at any position in the structure represented by the general formula (1) that constitutes Q (e.g., Ar 1 D, A, R 1 ~R 4 It can bond to either of the following. Two or more linking groups may be linked to one Q to form a cross-linked structure or a network structure.

[0052] As a concrete example of a repeating unit structure, we can cite the structure represented by the following formula. [ka]

[0053] Polymers having repeating units containing these formulas have any of the structures represented by general formula (1) (e.g., Ar 1 D, A, R 1 ~R 4It can be synthesized by introducing a hydroxyl group into one of the following ( ), using it as a linker to react with the following compounds to introduce polymerizable groups, and then polymerizing those polymerizable groups. [ka]

[0054] A polymer containing a structure represented by general formula (1) within its molecule may consist only of repeating units having the structure represented by general formula (1), or it may contain repeating units having other structures. Furthermore, the repeating units having the structure represented by general formula (1) contained in the polymer may be of a single type or two or more types. Examples of repeating units that do not have the structure represented by general formula (1) include those derived from monomers commonly used in copolymerization. For example, repeating units derived from monomers having ethylenically unsaturated bonds, such as ethylene and styrene, can be cited.

[0055] It is preferable that the compound represented by general formula (1) does not contain metal atoms. For example, a compound represented by general formula (1) can be selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms, oxygen atoms, and sulfur atoms. For example, a compound represented by general formula (1) can be selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms, and oxygen atoms. For example, a compound represented by general formula (1) can be selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms, and sulfur atoms. For example, a compound represented by general formula (1) can be selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, and nitrogen atoms. For example, a compound represented by general formula (1) can be selected from the group consisting of carbon atoms, hydrogen atoms, and nitrogen atoms.

[0056] In this specification, "alkyl group" may be linear, branched, or cyclic. Furthermore, two or more of the linear, cyclic, and branched portions may be mixed. The number of carbon atoms in the alkyl group can be, for example, 1 or more, 2 or more, or 4 or more. Also, the number of carbon atoms can be 30 or less, 20 or less, 10 or less, 6 or less, or 4 or less. Specific examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group, isohexyl group, 2-ethylhexyl group, n-heptyl group, isoheptyl group, n-octyl group, isooctyl group, n-nonyl group, isononyl group, n-decanyl group, isodecanyl group, cyclopentyl group, cyclohexyl group, and cycloheptyl group. The alkyl group substituent may be further substituted with an aryl group. The "alkenyl group" may be linear, branched, or cyclic. Furthermore, two or more of these linear, cyclic, and branched portions may be mixed. The number of carbon atoms in the alkenyl group can be, for example, 2 or more, 4 or more, or 30 or less, 20 or less, 10 or less, 6 or less, or 4 or less. Specific examples of alkenyl groups include ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, n-pentenyl, isopentenyl, n-hexenyl, isohexenyl, and 2-ethylhexenyl. The substituted alkenyl group may be further substituted with other substituents. The "aryl group" and "heteroaryl group" may be monorings or fused rings formed by the fusion of two or more rings. In the case of fused rings, the number of fused rings is preferably 2 to 6, and can be selected from, for example, 2 to 4. Specific examples of rings include benzene rings, pyridine rings, pyrimidine rings, triazine rings, naphthalene rings, anthracene rings, phenanthrene rings, triphenylene rings, quinoline rings, pyrazine rings, quinoxaline rings, and naphthyridine rings, and these may be fused rings. Specific examples of aryl groups or heteroaryl groups include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 2-pyridyl group, 3-pyridyl group, and 4-pyridyl group. The number of constituent atoms of the ring skeleton of the aryl group is preferably 6 to 40, more preferably 6 to 20, and can be selected within the range of 6 to 14 or within the range of 6 to 10. The number of constituent atoms in the ring skeleton of the heteroaryl group is preferably 4 to 40, more preferably 5 to 20, and may be selected within the range of 5 to 14 or within the range of 5 to 10. The terms "arylene group" and "heteroaryl group" can be used by changing the valency from 1 to 2 in the descriptions of the aryl group and heteroaryl group.

[0057] In this specification, "substituent group A" refers to a hydroxyl group, halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group (e.g., C1-40), alkoxy group (e.g., C1-40), alkylthio group (e.g., C1-40), aryl group (e.g., C6-30), aryloxy group (e.g., C6-30), arylthio group (e.g., C6-30), heteroaryl group (e.g., C5-30), heteroaryloxy group (e.g., C5-30), and This refers to one or more groups selected from the group consisting of teloarylthio groups (e.g., 5-30 ring skeleton atoms), acyl groups (e.g., 1-40 carbon atoms), alkenyl groups (e.g., 1-40 carbon atoms), alkynyl groups (e.g., 1-40 carbon atoms), alkoxycarbonyl groups (e.g., 1-40 carbon atoms), aryloxycarbonyl groups (e.g., 1-40 carbon atoms), heteroaryloxycarbonyl groups (e.g., 1-40 carbon atoms), silyl groups (e.g., trialkylsilyl groups with 1-40 carbon atoms), and nitro groups. In this specification, "substituent group B" means one or more groups selected from the group consisting of alkyl groups (e.g., 1 to 40 carbon atoms), alkoxy groups (e.g., 1 to 40 carbon atoms), aryl groups (e.g., 6 to 30 carbon atoms), aryloxy groups (e.g., 6 to 30 carbon atoms), heteroaryl groups (e.g., 5 to 30 atoms in the ring skeleton), heteroaryloxy groups (e.g., 5 to 30 atoms in the ring skeleton), and diarylaminoamino groups (e.g., 0 to 20 carbon atoms). In this specification, "substituent group C" means one or more groups selected from the group consisting of alkyl groups (e.g., 1 to 20 carbon atoms), aryl groups (e.g., 6 to 22 carbon atoms), heteroaryl groups (e.g., 5 to 20 atoms in the ring skeleton), and diarylamino groups (e.g., 12 to 20 carbon atoms). In this specification, "substituent group D" means one or more groups selected from the group consisting of alkyl groups (e.g., 1 to 20 carbon atoms), aryl groups (e.g., 6 to 22 carbon atoms), and heteroaryl groups (e.g., 5 to 20 atoms in the ring skeleton). In this specification, "substituent group E" means one group or a combination of two or more groups selected from the group consisting of alkyl groups (e.g., C1 to C20) and aryl groups (e.g., C6 to C22). In this specification, when a substituent is described as "substituent" or "substituted or unsubstituted," it may be selected from, for example, substituent group A, substituent group B, substituent group C, substituent group D, or substituent group E.

[0058] In one embodiment, the compound represented by general formula (1) is a light-emitting material. In one embodiment, the compound represented by general formula (1) is a compound that can emit delayed fluorescence. In some embodiments of this disclosure, a compound represented by general formula (1) can emit light in the UV region, the blue, green, yellow, orange, and red regions of the visible spectrum (e.g., about 420 nm to about 500 nm, about 500 nm to about 600 nm, or about 600 nm to about 700 nm) or the near-infrared region when excited by thermal or electronic means. In some embodiments of this disclosure, a compound represented by general formula (1) can emit light in the red or orange region of the visible spectrum (e.g., about 620 nm to about 780 nm, about 650 nm) when excited by thermal or electronic means. In some embodiments of this disclosure, a compound represented by general formula (1) can emit light in the orange or yellow region of the visible spectrum (e.g., about 570 nm to about 620 nm, about 590 nm, about 570 nm) when excited by thermal or electronic means. In some embodiments of this disclosure, a compound represented by general formula (1) can emit light in the green region of the visible spectrum (e.g., about 490 nm to about 575 nm, about 510 nm) when excited by thermal or electronic means. In some embodiments of this disclosure, a compound represented by general formula (1) can emit light in the blue region of the visible spectrum (e.g., about 400 nm to about 490 nm, about 475 nm) when excited by thermal or electronic means. In some embodiments of this disclosure, a compound represented by general formula (1) can emit light in the ultraviolet spectral region (e.g., 280-400 nm) when excited by thermal or electronic means. In some embodiments of this disclosure, a compound represented by general formula (1) can emit light in the infrared spectral region (e.g., 780 nm to 2 μm) when excited by thermal or electronic means. In some embodiments of this disclosure, organic semiconductor devices can be fabricated using compounds represented by general formula (1). For example, CMOS (complementary metal-oxide-semiconductor) devices can be fabricated using compounds represented by general formula (1). In some embodiments of this disclosure, organic optical devices such as organic electroluminescent devices and solid-state image sensors (e.g., CMOS image sensors) can be fabricated using compounds represented by general formula (1).

[0059] The electronic properties of small molecule chemical libraries can be calculated using known ab initio quantum chemical calculations. For example, the Hartree-Fock equation (TD-DFT / B3LYP / 6-31G*) can be analyzed using time-dependent density functional theory with 6-31G*, Becke's three parameters, and a group of functions known as the Lee-Yang-Parr hybrid functional as a basis, to screen for molecular fragments (parts) with HOMO above a certain threshold and LUMO below a certain threshold. As a result, for example, when there is a HOMO energy (e.g., ionization potential) of -6.5 eV or higher, the donor portion ("D") can be selected. Also, for example, when there is a LUMO energy (e.g., electron affinity) of -0.5 eV or lower, the acceptor portion ("A") can be selected. The bridge portion ("B") is a strongly conjugated system that can strictly restrict the acceptor and donor portions to specific stereochemistrys, thereby preventing duplication between the π-conjugated systems of the donor and acceptor portions. In one embodiment, the compound library is selected using one or more of the following characteristics: 1. Emission near a specific wavelength 2. The calculated triplet states above a specific energy level. 3. ΔE below a specific value ST value 4. Quantum yield above a specific value 5. HOMO levels 6. LUMO levels In one embodiment, the difference (ΔE) between the lowest singlet excited state and the lowest triplet excited state at 77K is ST ) is less than about 0.5 eV, less than about 0.4 eV, less than about 0.3 eV, less than about 0.2 eV, or less than about 0.1 eV. In one embodiment, ΔE ST The values ​​are less than approximately 0.09 eV, less than approximately 0.08 eV, less than approximately 0.07 eV, less than approximately 0.06 eV, less than approximately 0.05 eV, less than approximately 0.04 eV, less than approximately 0.03 eV, less than approximately 0.02 eV, or less than approximately 0.01 eV. In one embodiment, the compound represented by general formula (1) exhibits a quantum yield of more than 25%, for example, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, or higher.

[0060] [Method for synthesizing compounds represented by general formula (1)] The compound represented by general formula (1) is a novel compound. Compounds represented by general formula (1) can be synthesized by combining known reactions. For example, they can be synthesized using ring-closing reactions or substitution reactions. Specific synthesis conditions can be found in the synthesis examples described later.

[0061] [Constructions using compounds represented by general formula (1)] In some embodiments, the compound represented by general formula (1) is used in combination with one or more materials (e.g., small molecules, polymers, metals, metal complexes, etc.) that disperse the compound, covalently bond with the compound, coat the compound, support the compound, or associate with the compound to form a solid film or layer. For example, the compound represented by general formula (1) can be combined with an electroactive material to form a film. In some cases, the compound represented by general formula (1) may be combined with a hole transport polymer. In some cases, the compound represented by general formula (1) may be combined with an electron transport polymer. In some cases, the compound represented by general formula (1) may be combined with both a hole transport polymer and an electron transport polymer. In some cases, the compound represented by general formula (1) may be combined with a copolymer having both a hole transport portion and an electron transport portion. Through these embodiments, electrons and / or holes formed in a solid film or layer can be made to interact with the compound represented by general formula (1).

[0062] [Film formation] In one embodiment, a film containing the compound represented by general formula (1) of the present invention can be formed by a wet process. In the wet process, a solution of a composition containing the compound of the present invention is applied to a surface, and the film is formed after the solvent is removed. Examples of wet processes include, but are not limited to, spin coating, slit coating, inkjet (spray) printing, gravure printing, offset printing, and flexographic printing. In the wet process, a suitable organic solvent capable of dissolving the composition containing the compound of the present invention is selected and used. In one embodiment, substituents (e.g., alkyl groups) that increase the solubility in organic solvents can be introduced into the compound contained in the composition. In one embodiment, a film containing the compounds of the present invention can be formed by a dry process. In another embodiment, a vacuum deposition method can be used as the dry process, but is not limited to this. When a vacuum deposition method is used, the compounds constituting the film may be co-deposited from individual deposition sources, or from a single deposition source containing a mixture of compounds. When a single deposition source is used, a mixed powder of compound powders may be used, a compressed molded body obtained by compressing the mixed powder may be used, or a mixture obtained by heating, melting, and cooling each compound may be used. In one embodiment, by performing co-deposition under conditions where the deposition rates (weight loss rates) of multiple compounds contained in a single deposition source are the same or nearly the same, a film with a composition ratio corresponding to the composition ratio of multiple compounds contained in the deposition source can be formed. By mixing multiple compounds in the same composition ratio as the composition ratio of the formed film to create a deposition source, a film with a desired composition ratio can be easily formed. In one embodiment, the temperature at which each co-deposited compound has the same weight loss rate can be identified, and that temperature can be adopted as the temperature during co-deposition.

[0063] [Examples of the use of compounds represented by general formula (1)] Compounds represented by general formula (1) are useful as materials for organic light-emitting devices. They are particularly preferred for use in organic light-emitting diodes and the like. Organic light-emitting diodes: One aspect of the present invention relates to the use of a compound represented by general formula (1) as a light-emitting material for an organic light-emitting device. In some embodiments, the compound represented by general formula (1) can be effectively used as a light-emitting material in the light-emitting layer of an organic light-emitting device. In some embodiments, the compound represented by general formula (1) includes a delayed fluorescence (delayed phosphor) that emits delayed fluorescence. In some embodiments, the present invention provides a delayed phosphor having the structure represented by general formula (1). In some embodiments, the present invention relates to the use of a compound represented by general formula (1) as a delayed phosphor. In some embodiments, the compound represented by general formula (1) can be used as a host material and can be used together with one or more light-emitting materials, the light-emitting materials may be fluorescent materials, phosphorescent materials or TADFs. In some embodiments, the compound represented by general formula (1) can also be used as a hole transport material. In some embodiments, the compound represented by general formula (1) can be used as an electron transport material. In some embodiments, the present invention relates to a method for generating delayed fluorescence from a compound represented by general formula (1). In some embodiments, an organic light-emitting device containing the compound as a light-emitting material emits delayed fluorescence and exhibits high light emission efficiency. In one embodiment, the light-emitting layer contains a compound represented by general formula (1), and the compound represented by general formula (1) is oriented parallel to the substrate. In one embodiment, the substrate is a film-forming surface. In one embodiment, the orientation of the compound represented by general formula (1) relative to the film-forming surface affects or determines the direction of propagation of light emitted by the aligned compound. In one embodiment, the light extraction efficiency from the light-emitting layer is improved by aligning the direction of propagation of light emitted by the compound represented by general formula (1). One aspect of the present invention relates to an organic light-emitting device. In one embodiment, the organic light-emitting device includes a light-emitting layer. In one embodiment, the light-emitting layer includes a compound represented by general formula (1) as a light-emitting material. In one embodiment, the organic light-emitting device is an organic photoluminescent device (organic PL device). In one embodiment, the organic light-emitting device is an organic electroluminescent device (organic EL device). In one embodiment, the compound represented by general formula (1) assists the light emission of other light-emitting materials included in the light-emitting layer (as a so-called assist dopant). In one embodiment, the compound represented by general formula (1) included in the light-emitting layer is at its lowest excited singlet energy level and is located between the lowest excited singlet energy level of the host material included in the light-emitting layer and the lowest excited singlet energy level of the other light-emitting materials included in the light-emitting layer. In some embodiments, the organic photoluminescent element includes at least one light-emitting layer. In some embodiments, the organic electroluminescent element includes at least an anode, a cathode, and an organic layer between the anode and the cathode. In some embodiments, the organic layer includes at least a light-emitting layer. In some embodiments, the organic layer includes only a light-emitting layer. In some embodiments, the organic layer includes one or more organic layers in addition to the light-emitting layer. Examples of organic layers include hole transport layers, hole injection layers, electron barrier layers, hole barrier layers, electron injection layers, electron transport layers, and exciton barrier layers. In some embodiments, the hole transport layer may be a hole injection transport layer having a hole injection function, and the electron transport layer may be an electron injection transport layer having an electron injection function. An example of an organic electroluminescent element is shown in Figure 1.

[0064] Light-emitting layer: In one embodiment, the light-emitting layer is a layer in which holes and electrons injected from the anode and cathode, respectively, recombine to form excitons. In another embodiment, the layer emits light. In some embodiments, only the light-emitting material is used as the light-emitting layer. In some embodiments, the light-emitting layer includes the light-emitting material and a host material. In some embodiments, the light-emitting material is a compound represented by general formula (1). In some embodiments, singlet and triplet excitons generated in the light-emitting material are confined within the light-emitting material in order to improve the light emission efficiency of organic electroluminescent elements and organic photoluminescent elements. In some embodiments, a host material is used in addition to the light-emitting material in the light-emitting layer. In some embodiments, the host material is an organic compound. In some embodiments, the organic compound has excitation singlet energies and excitation triplet energies, at least one of which is higher than those of the light-emitting material of the present invention. In some embodiments, singlet and triplet excitons generated in the light-emitting material of the present invention are confined within the molecules of the light-emitting material of the present invention. In some embodiments, the singlet and triplet excitons are sufficiently confined to improve the light emission efficiency. In some embodiments, a host material that can achieve high light emission efficiency without being sufficiently confined, i.e., a host material that can achieve high light emission efficiency, even though high light emission efficiency can still be obtained, can be used in the present invention without particular limitation. In some embodiments, light emission occurs in the light-emitting material in the light-emitting layer of the device of the present invention. In some embodiments, the synchrotron radiation includes both fluorescence and delayed fluorescence. In some embodiments, the synchrotron radiation includes synchrotron radiation from a host material. In some embodiments, the synchrotron radiation consists of synchrotron radiation from a host material. In some embodiments, the synchrotron radiation includes synchrotron radiation from a compound represented by general formula (1) and synchrotron radiation from a host material. In some embodiments, a TADF molecule and a host material are used. In some embodiments, the TADF is an assist dopant, having a lower excitation singlet energy than the host material in the light-emitting layer and a higher excitation singlet energy than the light-emitting material in the light-emitting layer.

[0065] When a compound represented by general formula (1) is used as an assist dopant, various compounds can be used as the luminescent material (preferably a fluorescent material). Such luminescent materials include anthracene derivatives, tetracene derivatives, naphthacene derivatives, pyrene derivatives, perylene derivatives, chrysene derivatives, rubrene derivatives, coumarin derivatives, pyran derivatives, stilbene derivatives, fluorene derivatives, anthryl derivatives, pyromethene derivatives, terphenyl derivatives, terphenylene derivatives, fluorantene derivatives, amine derivatives, quinacridone derivatives, oxadiazole derivatives, malononitrile derivatives, pyran derivatives, carbazole derivatives, duroridine derivatives, thiazole derivatives, and derivatives having metals (Al,Zn). These exemplary skeletons may or may not have substituents. Furthermore, these exemplary skeletons may be combined with each other. The following are examples of luminescent materials that can be used in combination with an assist dopant having the structure represented by general formula (1).

[0066] [ka] [ka] [ka] [ka]

[0067] Furthermore, compounds described in paragraphs 0220-0239 of Publication No. WO2015 / 022974 and compounds having a pyrometenboron skeleton described in Publication No. WO2021 / 015177 can also be particularly preferred as luminescent materials used together with an assist dopant having a structure represented by general formula (1).

[0068] In one embodiment, when a host material is used, the amount of the compound of the present invention as a light-emitting material contained in the light-emitting layer is 0.1% by weight or more. In another embodiment, when a host material is used, the amount of the compound of the present invention as a light-emitting material contained in the light-emitting layer is 1% by weight or more. In another embodiment, when a host material is used, the amount of the compound of the present invention as a light-emitting material contained in the light-emitting layer is 50% by weight or less. In another embodiment, when a host material is used, the amount of the compound of the present invention as a light-emitting material contained in the light-emitting layer is 20% by weight or less. In another embodiment, when a host material is used, the amount of the compound of the present invention as a light-emitting material contained in the light-emitting layer is 10% by weight or less. In one embodiment, the host material of the light-emitting layer is an organic compound having hole transport and electron transport functions. In another embodiment, the host material of the light-emitting layer is an organic compound that prevents an increase in the wavelength of the synchrotron radiation. In yet another embodiment, the host material of the light-emitting layer is an organic compound having a high glass transition temperature.

[0069] In some embodiments, the host material is selected from the group consisting of: [ka] [ka] In one embodiment, the light-emitting layer contains two or more structurally different TADF molecules. For example, the light-emitting layer can contain three materials in which the excited singlet energy levels are highest in the host material, followed by the first TADF molecule and then the second TADF molecule. In this case, both the first and second TADF molecules have a difference ΔE between their lowest excited singlet energy level and the lowest excited triplet energy level of 77K. STThe luminescence voltage is preferably 0.3 eV or less, more preferably 0.25 eV or less, more preferably 0.2 eV or less, more preferably 0.15 eV or less, even more preferably 0.1 eV or less, even more preferably 0.07 eV or less, even more preferably 0.05 eV or less, even more preferably 0.03 eV or less, and particularly preferably 0.01 eV or less. The concentration of the first TADF molecules in the luminescent layer is preferably greater than the concentration of the second TADF molecules. Also, the concentration of the host material in the luminescent layer is preferably greater than the concentration of the second TADF molecules. The concentration of the first TADF molecules in the luminescent layer may be greater than, less than, or the same as the concentration of the host material. In one embodiment, the composition of the luminescent layer may be 10 to 70% by weight of the host material, 10 to 80% by weight of the first TADF molecules, and 0.1 to 30% by weight of the second TADF molecules. In one embodiment, the composition of the light-emitting layer may be 20-45% by weight of the host material, 50-75% by weight of the first TADF molecule, and 5-20% by weight of the second TADF molecule. In one embodiment, the photo-excited quantum emission yield φPL1(A) of a co-evaporated film of the first TADF molecule and the host material (concentration of the first TADF molecule in this co-evaporated film = A by weight) and the photo-excited quantum emission yield φPL2(A) of a co-evaporated film of the second TADF molecule and the host material (concentration of the second TADF molecule in this co-evaporated film = A by weight) satisfy the relationship φPL1(A)>φPL2(A). In another embodiment, the photo-excited quantum emission yield φPL2(B) of a co-evaporated film of the second TADF molecule and the host material (concentration of the second TADF molecule in this co-evaporated film = B by weight) and the photo-excited quantum emission yield φPL2(100) of a film of the second TADF molecule alone satisfy the relationship φPL2(B)>φPL2(100). In one embodiment, the light-emitting layer may contain three different structural TADF molecules. The compound of the present invention may be any of the multiple TADF compounds contained in the light-emitting layer. In some embodiments, the light-emitting layer may be composed of a material selected from the group consisting of a host material, an assist dopant, and a light-emitting material. In some embodiments, the light-emitting layer does not contain any metallic elements. In some embodiments, the light-emitting layer may be composed of a material consisting only of atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms, oxygen atoms, and sulfur atoms. Alternatively, the light-emitting layer may be composed of a material consisting only of atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms, and oxygen atoms. Alternatively, the light-emitting layer may be composed of a material consisting only of atoms selected from the group consisting of carbon atoms, hydrogen atoms, nitrogen atoms, and oxygen atoms. When the light-emitting layer contains a TADF material other than the compound of the present invention, the TADF material may be a known delayed fluorescence material. Preferred delayed fluorescence materials include paragraphs 0008-0048 and 0095-0133 of WO2013 / 154064, paragraphs 0007-0047 and 0073-0085 of WO2013 / 011954, paragraphs 0007-0033 and 0059-0066 of WO2013 / 011955, and paragraph 0008 of WO2013 / 081088. ~0071 and 0118~0133, paragraphs 0009~0046 and 0093~0134 of JP 2013-256490, paragraphs 0008~0020 and 0038~0040 of JP 2013-116975, paragraphs 0007~0032 and 0079~0084 of WO2013 / 133359, paragraph 0 of WO2013 / 161437 Paragraphs 008-0054 and 0101-0121 of Japanese Patent Publication No. 2014-9352, paragraphs 0007-0041 and 0060-0069 of Japanese Patent Publication No. 2014-9224, paragraphs 0008-0048 and 0067-0076 of Japanese Patent Publication No. 2017-119663, paragraphs 0013-0025 of Japanese Patent Publication No. 2017-119664, Japanese Patent Publication No. 2 This includes compounds included in the general formulas described in paragraphs 0012-0025 of Japanese Patent Publication No. 017-222623, paragraphs 0010-0050 of Japanese Patent Application Publication No. 2017-226838, paragraphs 0012-0043 of Japanese Patent Application Publication No. 2018-100411, and paragraphs 0016-0044 of Japanese Patent Application Publication No. WO2018 / 047853, particularly exemplary compounds that can emit delayed fluorescence.Furthermore, here we have Japanese Patent Publication No. 2013-253121, WO2013 / 133359, WO2014 / 034535, WO2014 / 115743, WO2014 / 122895, WO2014 / 126200, WO2014 / 136758, WO2014 / 133121, WO20 14 / 136860, WO2014 / 196585, WO2014 / 189122, WO2014 / 168101, WO2015 / 008 580 publication, WO2014 / 203840 publication, WO2015 / 002213 publication, WO2015 / 016200 publication, WO2015 / 019725 publication, Publications WO2015 / 072470, WO2015 / 108049, WO2015 / 080182, WO2015 / 072537, WO2015 / 080183, JP 2015-129240, WO2015 / 129714, WO2015 / 129715, WO2015 / 13350 A light-emitting material that can emit delayed fluorescence, as described in Publication No. 1, WO2015 / 136880, WO2015 / 137244, WO2015 / 137202, WO2015 / 137136, WO2015 / 146541, and WO2015 / 159541, can preferably be used. The above publications described in this paragraph are incorporated herein by reference as part of this specification.

[0070] The following describes each component of the organic electroluminescent element and each layer other than the light-emitting layer.

[0071] Base material: In some embodiments, the organic electroluminescent element of the present invention is held by a substrate, which is not particularly limited and may be any of the materials commonly used in organic electroluminescent elements, such as glass, transparent plastic, quartz, and silicon.

[0072] anode: In some embodiments, the anode of an organic electroluminescent apparatus is manufactured from a metal, alloy, conductive compound, or a combination thereof. In some embodiments, the metal, alloy, or conductive compound has a high work function (4 eV or more). In some embodiments, the metal is Au. In some embodiments, the conductive transparent material is selected from CuI, indium tin oxide (ITO), SnO2, and ZnO. In some embodiments, an amorphous material capable of forming a transparent conductive film, such as IDIXO (In2O3-ZnO), is used. In some embodiments, the anode is a thin film. In some embodiments, the thin film is manufactured by vapor deposition or sputtering. In some embodiments, the film is patterned by photolithography. In some embodiments, if the pattern does not need to be highly precise (e.g., about 100 μm or more), the pattern may be formed using a mask with a shape suitable for vapor deposition or sputtering onto the electrode material. In some embodiments, when a coating material such as an organic conductive compound can be applied, wet film formation methods such as printing or coating methods are used. In some embodiments, when synchrotron radiation passes through the anode, the anode has a transmittance of more than 10%, and the anode has a sheet resistance of several hundred ohms or less per unit area. In some embodiments, the thickness of the anode is 10 to 1,000 nm. In some embodiments, the thickness of the anode is 10 to 200 nm. In some embodiments, the thickness of the anode varies depending on the material used.

[0073] cathode: In some embodiments, the cathode is made of an electrode material such as a metal with a low work function (4 eV or less) (referred to as an electron-injection metal), an alloy, a conductive compound, or a combination thereof. In some embodiments, the electrode material is selected from sodium, sodium-potassium alloy, magnesium, lithium, magnesium-copper mixture, magnesium-silver mixture, magnesium-aluminum mixture, magnesium-indium mixture, aluminum-aluminum oxide (Al2O3) mixture, indium, lithium-aluminum mixture, and rare earth elements. In some embodiments, a mixture of the electron-injection metal and a second metal that is a stable metal having a higher work function than the electron-injection metal is used. In some embodiments, the mixture is selected from magnesium-silver mixture, magnesium-aluminum mixture, magnesium-indium mixture, aluminum-aluminum oxide (Al2O3) mixture, lithium-aluminum mixture, and aluminum. In some embodiments, the mixture improves electron-injection properties and resistance to oxidation. In some embodiments, the cathode is manufactured by forming the electrode material as a thin film by vapor deposition or sputtering. In some embodiments, the cathode has a sheet resistance of several hundred ohms or less per unit area. In some embodiments, the thickness of the cathode is 10 nm to 5 μm. In some embodiments, the thickness of the cathode is 50 to 200 nm. In some embodiments, either the anode or cathode of the organic electroluminescent element is transparent or translucent in order to transmit synchrotron radiation. In some embodiments, a transparent or translucent electroluminescent element enhances the light radiance. In some embodiments, a transparent or translucent cathode is formed by forming the cathode with respect to the conductive transparent material described above. In some embodiments, the element includes an anode and a cathode, both of which are transparent or translucent.

[0074] Injection layer: The injection layer is a layer between the electrode and the organic layer. In some embodiments, the injection layer reduces the driving voltage and enhances the light radiance. In some embodiments, the injection layer includes a hole injection layer and an electron injection layer. The injection layer can be located between the anode and the light-emitting layer or hole transport layer, and between the cathode and the light-emitting layer or electron transport layer. In some embodiments, an injection layer is present. In some embodiments, an injection layer is absent. The following are examples of preferred compounds that can be used as hole injection materials.

[0075] [ka]

[0076] Next, we will list some examples of preferred compounds that can be used as electron injection materials. [ka]

[0077] Barrier layer: A barrier layer is a layer that can prevent charges (electrons or holes) and / or excitons present in the light-emitting layer from diffusing to the outside of the light-emitting layer. In some embodiments, an electron barrier layer exists between the light-emitting layer and the hole transport layer, preventing electrons from passing through the light-emitting layer to the hole transport layer. In some embodiments, a hole barrier layer exists between the light-emitting layer and the electron transport layer, preventing holes from passing through the light-emitting layer to the electron transport layer. In some embodiments, a barrier layer prevents excitons from diffusing to the outside of the light-emitting layer. In some embodiments, the electron barrier layer and the hole barrier layer constitute an exciton barrier layer. As used herein, the terms “electron barrier layer” or “exciton barrier layer” include layers that have both the functions of an electron barrier layer and an exciton barrier layer.

[0078] Hole barrier layer: The hole barrier layer functions as an electron transport layer. In some embodiments, the hole barrier layer prevents holes from reaching the electron transport layer during electron transport. In some embodiments, the hole barrier layer increases the probability of electron-hole recombination in the light-emitting layer. The material used for the hole barrier layer may be the same material described above for the electron transport layer. The following are examples of preferred compounds that can be used in the hole barrier layer.

[0079] [ka]

[0080] Electron barrier layer: The electron barrier layer transports holes. In some embodiments, the electron barrier layer prevents electrons from reaching the hole transport layer during hole transport. In some embodiments, the electron barrier layer increases the probability of electron-hole recombination in the light-emitting layer. The material used for the electron barrier layer may be the same material described above for the hole transport layer. The following are specific examples of preferred compounds that can be used as electron barrier materials.

[0081] [ka]

[0082] Exciton barrier layer: The exciton barrier layer prevents excitons generated through the recombination of holes and electrons in the light-emitting layer from diffusing to the charge transport layer. In some embodiments, the exciton barrier layer enables effective confinement of excitons in the light-emitting layer. In some embodiments, the optical emission efficiency of the device is improved. In some embodiments, the exciton barrier layer is located on either the anode side or the cathode side and adjacent to the light-emitting layers on both sides. In some embodiments, when the exciton barrier layer is located on the anode side, it may be located between the hole transport layer and the light-emitting layer and adjacent to the light-emitting layer. In some embodiments, when the exciton barrier layer is located on the cathode side, it may be located between the light-emitting layer and the cathode and adjacent to the light-emitting layer. In some embodiments, a hole injection layer, electron barrier layer, or similar layer is located between the anode and the exciton barrier layer adjacent to the light-emitting layer on the anode side. In some embodiments, a hole injection layer, electron barrier layer, hole barrier layer, or similar layer is located between the cathode and the exciton barrier layer adjacent to the light-emitting layer on the cathode side. In some embodiments, the exciton barrier layer includes an excitation singlet energy and an excitation triplet energy, at least one of which is higher than the excitation singlet energy and excitation triplet energy of the luminescent material, respectively.

[0083] Hole transport layer: The hole transport layer comprises a hole transport material. In some embodiments, the hole transport layer is a single layer. In some embodiments, the hole transport layer has multiple layers. In some embodiments, the hole transport material has one of the following properties: hole injection or transport properties and electron barrier properties. In some embodiments, the hole transport material is an organic material. In some embodiments, the hole transport material is an inorganic material. Examples of known hole transport materials that can be used in the present invention include, but are not limited to, triazole derivatives, oxadiazole derivatives, imidazole derivatives, carbazole derivatives, indrocarbazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, allylamine derivatives, aminosubstituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers and conductive polymer oligomers (especially thiophene oligomers), or combinations thereof. In some embodiments, the hole transport material is selected from porphyrin compounds, aromatic tertiary amine compounds and styrylamine compounds. In some embodiments, the hole transport material is an aromatic tertiary amine compound. Specific examples of preferred compounds that can be used as hole transport materials are given below.

[0084] [ka]

[0085] Electron transport layer: The electron transport layer comprises an electron transport material. In some embodiments, the electron transport layer is a single layer. In some embodiments, the electron transport layer has multiple layers. In some embodiments, the electron transport material only needs to have the function of transporting electrons injected from the cathode to the light-emitting layer. In some embodiments, the electron transport material also functions as a hole barrier material. Examples of the electron transport layer that can be used in the present invention include, but are not limited to, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimide, fluorenylidene methane derivatives, anthraquinodimethane, anthrone derivatives, oxadiazole derivatives, azole derivatives, azine derivatives or combinations thereof, or polymers thereof. In some embodiments, the electron transport material is a thiadiazole derivative or a quinoxaline derivative. In some embodiments, the electron transport material is a polymer material. Specific examples of preferred compounds that can be used as the electron transport material are given below.

[0086]

Chemical formula

[0087] Furthermore, preferred compound examples of materials that can be added to each organic layer are given. For example, it is conceivable to add it as a stabilizing material or the like.

[0088]

Chemical formula

[0089] Although preferred materials that can be used in the organic electroluminescence device have been specifically exemplified, the materials that can be used in the present invention should not be construed as being limited to the following exemplified compounds. Also, even the compounds exemplified as materials having a specific function can be diverted as materials having other functions.

[0090] ​​​​ In some embodiments, the electronic device includes an OLED having an anode, a cathode, and at least one organic layer including a light-emitting layer between the anode and the cathode. In some embodiments, the components described herein can be incorporated into various photosensitive or photoactivated devices, such as OLEDs or optoelectronic devices. In some embodiments, the components may be useful for facilitating charge transfer or energy transfer within the device and / or as hole transport materials. Examples of such devices include organic light-emitting diodes (OLEDs), organic integrated circuits (OICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field-quench devices (O-FQDs), light-emitting fuel cells (LECs), or organic laser diodes (O-lasers).

[0091] Bulb or lamp: In some embodiments, the electronic device includes an OLED comprising an anode, a cathode, and at least one organic layer including a light-emitting layer between the anode and the cathode. In some embodiments, the device includes OLEDs of different colors. In some embodiments, the device includes an array comprising combinations of OLEDs. In some embodiments, the combination of OLEDs is a combination of three colors (e.g., RGB). In some embodiments, the combination of OLEDs is a combination of colors other than red, green, and blue (e.g., orange and yellow-green). In some embodiments, the combination of OLEDs is a combination of two, four, or more colors. In some embodiments, the device is A circuit board having a first surface with a mounting surface and a second surface opposite to it, defining at least one opening, The mounting surface comprises at least one OLED having a light-emitting configuration, wherein the at least one OLED includes an anode, a cathode, and at least one organic layer comprising a light-emitting layer between the anode and the cathode, A housing for a circuit board, An OLED light comprising at least one connector located at the end of the housing, wherein the housing and the connector define a package suitable for mounting to a lighting fixture. In some embodiments, the OLED light has multiple OLEDs mounted on a circuit board such that light is emitted in multiple directions. In some embodiments, some of the light emitted in the first direction is polarized and emitted in a second direction. In some embodiments, a reflector is used to polarize the light emitted in the first direction.

[0092] Display or screen: In some embodiments, the light-emitting layer of the present invention can be used in a screen or display. In some embodiments, the compound according to the present invention is deposited on a substrate using a process such as vacuum evaporation, deposition, vapor deposition, or chemical vapor deposition (CVD), but is not limited. In some embodiments, the substrate is a photoplate structure useful in two-sided etching, providing pixels with a unique aspect ratio. The screen (also called a mask) is used in the manufacturing process of an OLED display. The design of the corresponding artwork pattern allows for the arrangement of very steep, narrow tie bars between pixels in the vertical direction, as well as large, wide oblique apertures in the horizontal direction. This enables the fine pattern configuration of pixels required for high-resolution displays, while optimizing chemical vapor deposition on a TFT backplane. Internal patterning of pixels allows for the creation of three-dimensional pixel apertures with various aspect ratios in the horizontal and vertical directions. Furthermore, the use of imaged "stripes" or halftone circles within a pixel area protects etching in specific areas until these particular patterns are undercut and removed from the substrate. At that time, all pixel areas are processed at a similar etching rate, but the depth varies depending on the halftone pattern. By changing the size and spacing of the halftone patterns, etching with varying degrees of protection within the pixel becomes possible, enabling localized deep etching necessary to form steep vertical bevels. A preferred material for deposition masks is Invar. Invar is a metal alloy that is cold-rolled into long, thin sheets at steel mills. Invar cannot be electrodeposited onto a spin mandrel as a nickel mask. A suitable and low-cost method for forming openings within a deposition mask is by wet chemical etching. In some embodiments, the screen or display pattern is a pixel matrix on a substrate. In some embodiments, the screen or display pattern is fabricated using lithography (e.g., photolithography and e-beam lithography). In some embodiments, the screen or display pattern is fabricated using wet chemical etching. In further embodiments, the screen or display pattern is fabricated using plasma etching.

[0093] Device manufacturing method: OLED displays are generally manufactured by forming a large mother panel and then cutting the mother panel into cell panels. Typically, each cell panel on the mother panel is formed by forming a thin-film transistor (TFT) having an active layer and source / drain electrodes on a base substrate, coating the TFT with a planarization film, sequentially forming pixel electrodes, an emissive layer, a counter electrode, and an encapsulation layer over time, and then cutting it from the mother panel. OLED displays are generally manufactured by forming a large mother panel and then cutting the mother panel into cell panels. Typically, each cell panel on the mother panel is formed by forming a thin-film transistor (TFT) having an active layer and source / drain electrodes on a base substrate, coating the TFT with a planarization film, sequentially forming pixel electrodes, an emissive layer, a counter electrode, and an encapsulation layer over time, and then cutting it from the mother panel.

[0094] In another aspect of the present invention, a method for manufacturing an organic light-emitting diode (OLED) display is provided, the method being A process of forming a barrier layer on the base substrate of the mother panel, The process of forming multiple display units on the barrier layer in cell panel units, The process of forming an encapsulation layer on each of the display units of the cell panel, The process includes the step of applying an organic film to the interface portion between the cell panels. In some embodiments, the barrier layer is an inorganic film formed of, for example, SiNx, and the edges of the barrier layer are covered with an organic film formed of polyimide or acrylic. In some embodiments, the organic film assists in the soft cutting of the mother panel into cell panel units. In some embodiments, the thin-film transistor (TFT) layer includes a light-emitting layer, a gate electrode, and source / drain electrodes. Each of a plurality of display units may include a thin-film transistor (TFT) layer, a planarization film formed on the TFT layer, and a light-emitting unit formed on the planarization film, wherein the organic film coated on the interface portion is formed of the same material as the planarization film and is formed simultaneously with the formation of the planarization film. In some embodiments, the light-emitting unit is connected to the TFT layer by a passivation layer, a planarization film between them, and an encapsulation layer that covers and protects the light-emitting unit. In some embodiments of the manufacturing method, the organic film is not connected to the display unit or the encapsulation layer.

[0095] Each of the organic film and the planarization film may contain either polyimide or acrylic. In some embodiments, the barrier layer may be an inorganic film. In some embodiments, the base substrate may be formed of polyimide. The method may further include the steps of attaching a carrier substrate made of glass material to another surface of the base substrate before forming a barrier layer on one surface of the polyimide base substrate, and separating the carrier substrate from the base substrate before cutting along the interface. In some embodiments, the OLED display is a flexible display. In some embodiments, the passivation layer is an organic film placed on the TFT layer for coating the TFT layer. In some embodiments, the planarization film is an organic film formed on the passivation layer. In some embodiments, the planarization film is made of polyimide or acrylic, as is the organic film formed at the edges of the barrier layer. In some embodiments, the planarization film and the organic film are formed simultaneously during the manufacture of the OLED display. In some embodiments, the organic film may be formed at the edges of the barrier layer, so that a portion of the organic film is in direct contact with the base substrate, and the remaining portion of the organic film is in contact with the barrier layer while surrounding the edges of the barrier layer.

[0096] In some embodiments, the light-emitting layer includes a pixel electrode, a counter electrode, and an organic light-emitting layer disposed between the pixel electrode and the counter electrode. In some embodiments, the pixel electrode is connected to the source / drain electrodes of the TFT layer. In some embodiments, when a voltage is applied to the pixel electrode through the TFT layer, an appropriate voltage is formed between the pixel electrode and the counter electrode, causing the organic light-emitting layer to emit light, thereby forming an image. Hereinafter, an image forming unit having a TFT layer and a light-emitting unit will be referred to as a display unit. In some embodiments, the encapsulation layer that covers the display unit and prevents the penetration of external moisture may be formed into a thin-film encapsulation structure in which an organic film and an inorganic film are alternately laminated. In some embodiments, the encapsulation layer has a thin-film encapsulation structure in which a plurality of thin films are laminated. In some embodiments, the organic film applied to the interface portion is disposed at intervals from each of the plurality of display units. In some embodiments, the organic film is formed in such a manner that some of the organic film directly contacts the base substrate, and the remaining portion of the organic film surrounds the end portion of the barrier layer while contacting the barrier layer.

[0097] In one embodiment, the OLED display is flexible and uses a flexible base substrate formed of polyimide. In some embodiments, the base substrate is formed on a carrier substrate formed of a glass material, and then the carrier substrate is separated. In some embodiments, the barrier layer is formed on the surface of the base substrate on the opposite side of the carrier substrate. In one embodiment, the barrier layer is patterned according to the size of each cell panel. For example, while the base substrate is formed on all surfaces of the mother panel, the barrier layer is formed according to the size of each cell panel, whereby grooves are formed in the interface portion between the barrier layers of the cell panels. Each cell panel can be cut along the grooves.

[0098] In some embodiments, the manufacturing method further includes a step of cutting along the interface portion, where a groove is formed in the barrier layer, and at least a portion of the organic film is formed in the groove, and the groove does not penetrate the base substrate. In some embodiments, a TFT layer is formed for each cell panel, and a passivation layer, which is an inorganic film, and a planarization film, which is an organic film, are placed on the TFT layer and cover the TFT layer. At the same time that a planarization film made of, for example, polyimide or acrylic is formed, the groove in the interface portion is covered with an organic film made of, for example, polyimide or acrylic. This prevents cracking by allowing the organic film to absorb the impact generated when each cell panel is cut along the groove at the interface portion. That is, if all barrier layers are completely exposed without an organic film, when each cell panel is cut along the groove at the interface portion, the impact generated is transmitted to the barrier layer, thereby increasing the risk of cracking. However, in one embodiment, the groove in the interface portion between barrier layers may be covered with an organic film to absorb the impact that would otherwise be transmitted to the barrier layer, so that each cell panel is cut softly and cracking in the barrier layer is prevented. In one embodiment, the organic film and the planarizing film covering the grooves of the interface portion are arranged with a gap between them. For example, if the organic film and the planarizing film are connected to each other as a single layer, there is a risk that external moisture may penetrate the display unit through the remaining parts of the planarizing film and organic film. Therefore, the organic film and the planarizing film are arranged with a gap between them so that the organic film is spaced away from the display unit.

[0099] In some embodiments, the display unit is formed by the formation of a light-emitting unit, and an encapsulation layer is placed on the display unit to cover it. This separates the carrier substrate supporting the base substrate from the base substrate after the mother panel is completely manufactured. In some embodiments, when a laser beam is emitted onto the carrier substrate, the carrier substrate is separated from the base substrate due to the difference in thermal expansion coefficients between the carrier substrate and the base substrate. In some embodiments, the mother panel is cut into cell panel units. In some embodiments, the mother panel is cut along the interface between cell panels using a cutter. In some embodiments, the grooves of the interface along which the mother panel is cut are covered with an organic film so that the organic film absorbs the impact during cutting. In some embodiments, cracking can be prevented in the barrier layer during cutting. In some embodiments, the method reduces the defect rate of the product and stabilizes its quality. Another embodiment is an OLED display having a barrier layer formed on a base substrate, a display unit formed on the barrier layer, an encapsulation layer formed on the display unit, and an organic film coated on the edges of the barrier layer. [Examples]

[0100] The features of the present invention will be further described in detail below with reference to synthesis examples and embodiments. The materials, processing content, processing procedures, etc. shown below can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the specific examples shown below. The luminescence characteristics were evaluated using a source meter (Keithley Corporation: 2400 series), a semiconductor parameter analyzer (Agilent Technologies: E5273A), an optical power meter measuring device (Newport Corporation: 1930C), an optical spectrometer (Ocean Optics: USB2000), a spectroradiometer (Topcon Corporation: SR-3), and a streak camera (Hamamatsu Photonics K.K.: C4334).

[0101] (Synthesis Example 1) Synthesis of Compound 53 [ka]

[0102] Under a nitrogen atmosphere, 3-fluoro-4-nitrobenzonitrile (1.38 g, 10.0 mmol) and 1-fluorocarbazole (0.93 g, 5.0 mmol) were reacted in dimethylformamide (30 mL) in the presence of potassium carbonate at 50°C for 2.5 hours. The reaction was then stopped at room temperature with water. The precipitated solid was filtered, the filtrate was dissolved in ethyl acetate, dried over magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The resulting reaction mixture was purified by silica gel column chromatography (ethyl acetate / hexane = 4 / 1) and reprecipitation (ethyl acetate / hexane) to obtain compound b (1.67 g, 99% yield) as a yellow solid. 1 H NMR (400MHz,CDCl3,δ): 8.29 (d, J= 10 Hz, 1H), 8.11 (d, J = 10 Hz, 1H), 8.0 (s, 1H), 7.95 (d, J = 10 Hz, 1H), 7.89 (d, J = 10 Hz, 1H), 7.44 (t, J = 10 Hz, 1H), 7.35 (t, J = 10 Hz, 1H), 7.24 (m, 1H), 7.12 (t, J = 10.0 Hz, 1H), 7.07 (t, J = 10.0 Hz, 1H). MS (ASAP): 331.08 (M+H + Calcd for C 50 H 37 N5: 332.17.

[0103] Under a nitrogen atmosphere, compound b (1.38 g, 10.0 mmol), activated carbon (0.18 g, 15.0 mmol), and iron chloride (0.135 g, 0.5 mmol) were dissolved in a mixed solvent of toluene (150 mL) and ethanol (150 mL), and aqueous hydrazine solution (4 ml, 125 mmol) was added. The reaction mixture was reacted at 90°C for 2 hours, then allowed to cool to room temperature and filtered by Celite. The solvent was removed by vacuum distillation, water and ethyl acetate were added, and after extraction, the organic layer was separated. The layer was dried over magnesium sulfate, and the solvent was removed by vacuum distillation. The filtrate was dissolved in ethyl acetate, dried over magnesium sulfate, and the solvent was removed by vacuum distillation. The obtained reaction mixture was purified by silica gel column chromatography (ethyl acetate / hexane = 1 / 1) and reprecipitation (ethyl acetate / hexane) to obtain compound c (1.35 g, yield 90%) as a white solid. 1 H NMR (400MHz,CDCl3,δ): 8.21 (d, J= 10 Hz, 1H), 8.02 (m, 1H), 7.40 (t, J = 10 Hz, 1H), 7.26 (d, J = 10 Hz, 2H), 7.18 (m, 3H), 6.97 (d, J = 10 Hz, 1H), 7.93 (d, J = 10.0 Hz, 1H), 5.48 (s, 1H). MS (ASAP): 301.10 (M+H + Calcd for C 50 H 37 N5: 302.17.

[0104] [ka]

[0105] Under a nitrogen atmosphere, compound c (0.75 g, 2.5 mmol), compound d (1.0 g, 2.17 mmol), tri(tert-butyl)phosphonium tetrafluoroborate (95 mg, 0.325 mmol), cesium carbonate (1.41 g, 4.34 mmol), and trisdibenzylideneacetone bispalladium (100 mg, 0.168 mmol) were reacted in toluene (200 mL) at 130 °C for 24 hours. The reaction was stopped by pouring the reaction solution into water at room temperature. Dichloromethane was added, and the organic layer was separated by extraction. The mixture was then dried over magnesium sulfate, and the solvent was removed by vacuum distillation. The resulting residue was purified by column chromatography (toluene) to obtain compound e (0.7 g, 63%) as a yellow solid. 1 H NMR (400MHz,CDCl3,δ): 9.46 (m, 3H), 9.32 (d, J = 10 Hz, 1H), 8.87 (t, J = 10 Hz, 3H), 8.54 (m, 1H), 8.46 (s, 1H), 8.25 (d, J = 10 Hz, 1H), 8.10 (d, J = 10.0 Hz, 1H), 7.97 (s, 1H), 7.88 (m, 8H), 7.70 (d, J = 10.0 Hz, 1H), 7.46 (t, J= 10.0 Hz, 1H), 7.28 (m, 3H). MS (ASAP): 679.22(M+H + Calcd for C 50 H 37 N5: 680.35.

[0106] Compound e (0.7 g, 1.02 mmol) and sodium hydride (45 mg, 1.1 mmol) were reacted in dimethylformamide (50 mL) at 150 °C for 24 hours. The reaction solution was allowed to cool to room temperature, water was added, and the resulting solid was filtered off, washed, dissolved in toluene, dried over magnesium sulfate, and the solvent was concentrated by vacuum distillation. The resulting residue was purified by column chromatography (toluene) and reprecipitation (chloroform / methanol) to obtain compound 53 (0.27 g, 57%), a yellow solid. MS (ASAP): 659.21(M+H+ Calcd for C 50 H 37 N5: 660.09.

[0107] (Synthesis Example 2) Synthesis of Compound 3054 [ka]

[0108] Under a nitrogen atmosphere, a mixture of 2-(6-bromo-1-fluoro-9H-carbazole-9-yl)aminobenzene (19.0 g, 53.5 mmol) and copper(I) cyanide (14.4 g, 161 mmol) was mixed with N-methyl-2-pyrrolidone (NMP, 900 mL) and stirred at 170°C for 48 hours. The reaction solution was allowed to cool to room temperature, water was added, and the mixture was filtered. The crude product was purified by silica gel column chromatography (hexane:ethyl acetate = 4:1) to obtain 12.0 g (39.8 mmol, yield 74%) of compound f as a white solid. 1 H-NMR (400 MHz, DMSO-d6): δ 8.87 (s, 1H), 8.21-8.17 (m, 1H), 7.33-7.28 (m, 2H), 7.25 (t, J = 8 Hz, 1H), 7.14 (d, J = 8 Hz, 1H), 6.93 (d, J = 8 Hz, 1H), 6.67 (t, J = 8 Hz, 1H), 5.05 (s, 1H). MS (ASAP): 302.48(M+H + Calcd for C 19 H 12 FN3: 301.10.

[0109] [ka]

[0110] Under a nitrogen atmosphere, 4,5-dibromo-1,2-phenylenediamine (4.0 g, 15 mmol) and 4-tert-butylphenylboronic acid (6.7 g, 38 mmol) were dissolved in toluene (130 mL), ethanol (10 mL), and water (20 mL). Potassium carbonate (8.3 g, 60 mmol) and bis(triphenylphosphine)palladium(II) dichloride (0.26 g, 0.4 mmol) were added, and the mixture was stirred at 90°C for 24 hours. The reaction solution was allowed to return to room temperature, extracted with chloroform, and dried over anhydrous magnesium sulfate. The solvent was removed by distillation, and the compound was purified by silica gel column chromatography to obtain 4.5 g (12 mmol, yield 80%) of a white solid compound. MS (ASAP): 373(M+H + Calcd for C 26 H 32 N2: 372.

[0111] Under a nitrogen atmosphere, a mixture of compound g (5.00 g, 13.4 mmol) and 3-bromophenanthrene-9,10-dione (3.85 g, 13.4 mmol) was mixed with acetic acid (200 mL) and stirred at 130 °C for 24 hours. The reaction solution was allowed to return to room temperature, methanol was added, and the mixture was filtered. The crude product was washed with methanol and chloroform to obtain compound h (7.5 g, 12 mmol, 90% yield), a white-yellow solid. MS (ASAP): 623 (M+H + Calcd for C 40 H 35 BrN2: 622.

[0112] Under a nitrogen atmosphere, compound h (3.8 g, 6.1 mmol) and compound f (2.0 g, 6.7 mmol) were dissolved in toluene (160 mL). Tri-tert-butylphosphonium tetrafluoroborate (0.56 g, 1.2 mmol), cesium carbonate (4.0 g, 12 mmol), and tris(dibenzylideneacetone)dipalladium (0) (0.56 g, 0.61 mmol) were added, and the mixture was stirred at 120 °C for 15 hours. The reaction solution was allowed to cool to room temperature, extracted with chloroform, and dried over anhydrous magnesium sulfate. The solvent was removed by distillation, and the mixture was purified by silica gel column chromatography (hexane:toluene = 3:7) to obtain compound i (1.0 g, 1.2 mmol, yield 19%) as a yellow solid. 1 H-NMR(400MHz,CDCl3): δ 9.390 (dd, J = 7.2 Hz, 3.2 Hz, 2H), 9.187 (d, J = 8.8 Hz, 1H), 8.418 (s, 1H), 8.335-8.300 (m, 3H), 8.030 (s, 1H), 7.903 (dd, J = 8.0 Hz, 1.2 Hz, 1H), 7.760-7.718 (m, 3H), 7.695 (dd, J = 8.0 Hz, 1.2 Hz, 1H), 7.557 (td, J = 8.8 Hz, 1.6 Hz, 1H), 7.450 (d, J = 7.6 Hz, 1H), 7,331-7.212 (m, 13H), 5.705 (s, 1H), 1.334 (s, 18H). MS (ASAP): 844.30 (M+H + Calcd for C 59 H 46 FN5: 843.37. ASAP MS spectral analysis: C 59 H 46 FN5: Theoretical value 843.37, Observed value 844.30 [M+H + ]

[0113] A mixture of NaH (28 mg, 0.69 mmol) and compound i (0.53 g, 0.63 mmol) in 50 mL of N,N-dimethylformamide was stirred at 150°C for 15 hours. The mixture was allowed to return to room temperature, quenched with water, and the precipitated solid was filtered and washed with methanol. The resulting solid was purified by silica gel column chromatography to obtain compound 3054 (0.45 g, 0.55 mmol, yield 87%). 1 H-NMR (400 MHz, CDCl3): δ 9.725 (d, J = 8.0 Hz, 1H), 9.484 (d, J = 8.8 Hz, 1H), 8.635 (s, 1H), 8.524 (d, J = 9.2 Hz, 1H), 8.418 (d, J = 3.2 Hz, 2H), 8.353 (s, 1H), 8.084 (d, J = 9.2 Hz, 1H), 7.833-7.755 (m, 4H), 7.722 (d, J = 8.4 Hz, 1H), 7.336 (d, J = 8.4Hz, 4H), 7.275-7.259 (m, 5H), 6.902-6.746 (m, 3H), 6.304 (d, J = 8.4 Hz, 1H), 5.946 (d, J = 7.6 Hz, 1H), 1.352 (s, 18H). MS (ASAP): 824.52 (M+H + Calcd for C 59 H 45 N5: 823.37.

[0114] (Synthesis Example 2) Synthesis of Compound 17254 [ka]

[0115] Under a nitrogen atmosphere, compound j (1.83 g, 5.74 mmol), compound k (1.85 g, 5.74 mmol), triethylamine (3.4 mL), acetic acid (100 mL), and ethanol (25 mL) were stirred at 130°C for 6 hours. After the mixture was allowed to return to room temperature, the precipitated solid was filtered. The residue was washed with methanol to obtain compound l (2.25 g, 3.95 mmol, 70% yield). MS (ASAP): 570. Calcd for C 36 H 31 BrN2:570.

[0116] [ka]

[0117] Under a nitrogen stream, compound l (2.0 g, 3.4 mmol), compound m (1.2 g, 3.8 mmol), tBu3PHBF4 (0.1 g, 0.34 mmol), and tBuONa (0.8 g, 6.8 mmol) were dissolved in toluene (300 mL), to which Pd2dba3 (0.16 g, 0.17 mmol) was added, and the mixture was heated under reflux overnight. After the reaction solution was allowed to return to room temperature, water was added to quench it, and the mixture was extracted with dichloromethane. The solvent was removed by evaporation, and the compound was purified by silica gel column chromatography to obtain compound n (2.2 g, 2.8 mmol, yield 82%). MS (ASAP): 791. Calcd for C 55 H 42 FN5:791.

[0118] [ka]

[0119] Under a nitrogen atmosphere, a solution of compound n (2.0 g, 2.5 mmol) in N,N-dimethylformamide (200 mL) was mixed with NaH (0.3 g, 7.6 mmol) and stirred at 150 °C for 2 hours. After the reaction solution was allowed to return to room temperature, water was added to quench the mixture, and the precipitated solid was filtered. The residue was washed with methanol and further purified by silica gel column chromatography to obtain compound 17254 (0.8 g, 1.03 mmol, yield 42%). MS (ASAP): 771. Calcd for C 55 H 41 N5:771.

[0120] (Example 1) Thin film fabrication and evaluation Vacuum deposition onto a quartz substrate, with a vacuum level of 1 × 10⁻⁶ -3 Compound 53 was deposited under conditions of less than Pa, forming a thin film consisting solely of compound 53 with a thickness of 100 nm, which was the neat thin film of Example 1. Separately, a vacuum deposition method was used on a quartz substrate to create a thin film with a vacuum of 1 × 10⁻⁶. -3 Compound 53 and mCBP were deposited from different deposition sources under conditions below Pa, forming a thin film with a compound 53 concentration of 20% by weight and a thickness of 100 nm, which was used as the doped thin film of Example 1. The doped thin film of Example 1 had an emission peak wavelength of 594 nm, and both immediate fluorescence and delayed fluorescence were observed. The lifetime τ2 of the delayed fluorescence was 5.1 μs, confirming that it possessed excellent properties. Instead of compound 53, neat thin films and doped thin films can be obtained using compound 3054, compound 17254, and other compounds represented by general formula (1), and their properties can be confirmed. Compounds represented by general formula (1) achieve high PLQY in highly doped thin films. Therefore, by using them in organic light-emitting devices, it is possible to provide devices with high luminous efficiency and good durability.

[0121] (Example 2) Fabrication and evaluation of an organic electroluminescent device Each thin film is deposited onto a glass substrate with an anode made of indium tin oxide (ITO) with a thickness of 100 nm using a vacuum deposition method at a vacuum level of 1 × 10⁻⁶. -6The layers were stacked using Pa. First, HATCN was formed to a thickness of 10 nm on ITO, and then NPD was formed on top of it to a thickness of 30 nm. Next, TrisPCz was formed to a thickness of 10 nm on top of that, and then Host1 was formed to a thickness of 5 nm on top of that. Then, compound 53 and Host1 were co-deposited from different deposition sources to form a 30 nm thick light-emitting layer. At this time, the concentration of compound 53 was 35 wt%. On top of that, SF3TRZ was formed to a thickness of 10 nm, and then SF3TRZ and Liq were co-deposited from different deposition sources to form a 30 nm thick layer. At this time, the SF3TRZ:Liq (weight ratio) was 7:3. Furthermore, Liq was formed to a thickness of 2 nm, and then aluminum (Al) was deposited to a thickness of 100 nm to form the cathode. Following the above procedure, the organic electroluminescent device of Example 1 was fabricated. Furthermore, instead of compound 53, each organic electroluminescent element can be fabricated using compound 3054, compound 17254, or other compounds represented by general formula (1) following the same procedure, and their effects can be confirmed.

[0122] [ka] [Explanation of symbols]

[0123] 1 Base material 2 Anode 3. Hole injection layer 4. Hole transport layer 5. Emitting layer 6 Electron transport layer 7 Cathode

Claims

1. A compound represented by the following general formula (4a). General formula (4a) 【Chemistry 1】 In general formula (4a), R ２１ ~R 28 each independently represents a hydrogen atom, a deuterium atom, or D. However, R ２１ ~R ２８ One of these is D, and D represents the group represented by the following general formula (2). R ２９ ~R 36 each independently represents a hydrogen atom, a deuterium atom, or an alkyl group. General formula (2) 【Chemistry 2】 In general formula (2), R ５ and R ６ 、R ６ and R ７ 、R ８ and R ９ 、R ９ and R １０ 、R １０ and R １１ 、R １１ and R １２ 、R １２ and R １３ 、R １３ and R １４ 、R １４ and R １５ do not combine with each other to form a cyclic structure. R5 to R １５ each independently represents a hydrogen atom, a deuterium atom or a cyano group. However, at least one of R ５ to R １５ is a cyano group. X represents a single bond. * represents the bonding position.

2. A light-emitting material comprising the compound described in claim 1.

3. A film containing the compound described in claim 1.

4. An organic semiconductor device comprising the compound described in claim 1.

5. An organic light-emitting element comprising the compound described in claim 1.

6. The organic light-emitting element according to claim 5, wherein the element has a layer containing the compound, and the layer also contains a host material.

7. The organic light-emitting element according to claim 6, wherein the layer containing the compound also contains a delayed fluorescence material in addition to the host material, and the lowest excitation singlet energy of the delayed fluorescence material is lower than that of the host material and higher than that of the compound.

8. The organic light-emitting element according to claim 5, wherein the element has a layer containing the compound, and the layer also includes a light-emitting material having a structure different from that of the compound.

9. The organic light-emitting element according to any one of claims 5 to 7, wherein the material contained in the element has the greatest amount of light emitted from the compound.

10. The organic light-emitting element according to claim 8, wherein the amount of light emitted from the light-emitting material is greater than the amount of light emitted from the compound.

11. An organic light-emitting element according to any one of claims 5 to 10, which emits delayed fluorescence.

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